A very large amount of shoujo is based on this trope, where the extremely handsome and cynical male lead falls for the honest, down-to-earth female lead because he can't wrap her around his finger as easily as he can everyone else. Sometimes even used when it makes no sense because the heroine does fall for everything, because she's supposed to be the self-insert and the audience is supposed to find the lead so irresistible.
Mao became a Yandere because of this trope, as C.C. ended up being the only person he could have extended contact with that wouldn't fill up his head with the white noise created by his uncontrollableGeass power.
Lelouch/C.C. shippers will argue along these lines as well. Not because of Lelouch's Geass power so much as that she's too experienced to be in awe of him, though she is his closest ally. It is less a lack of control, as much as it is an independent streak and dependency on each other that make them partners, and not merely a subordinate.
A mostly mundane version of this seems to be what attracts most of the suitors of Shuurei in Saiunkoku Monogatari. Being a confident, outspoken, and blindingly intelligent woman in an otherwise male-dominated society, she doesn't let ANY level of authority or nobility intimidate her, up to and including the Emperor himself. As a result, several of the most powerful men in the Empire become enamoured with her straightforward and willful personality, whether it be a fatherly concern or outright true love.
In One Piece, part of the reason why Boa Hancock falls in love with Luffy if due to the fact that he's the only one who can resist her charms, while everyone else she comes in contact falls head over heels for her.
One of the reasons Iason is so attracted to Riki in Ai no Kusabi is the latter's rebellious nature and defiant pride. The more Riki fights and resists him, Iason becomes more excited and determined to get Riki to submit willingly.
Ali Filler Villain of the "Makaiju/Doom Tree arc" in the anime specifically states to himself after Usagi runs away after he failed in his attempt at wooing her that "Every time she runs away it only heightens my determination to win her over..."
Prince Dimando likes Usagi's Older and Wiser self, Queen Serenity, for this reason as well. When Usagi reacts in the same manner, he also pursues her.
Count Germont from Honoo No Alpen Rose is repeteadly rejected by the heroine Jeudi, but he keeps trying to make her his mistress no matter what. Lampshaded by the Count's wife Francoise, who tells Jeudi that the Count's impressed by Jeudi's ability to tell him no repeatedly, and confesses that she also envies Jeudi for it.
Reimei No Arcana: One of the first few things that attracts Caesar to (and annoys him about) Nakaba is her refusal to be controlled by him.
Pandora Hearts: In spite of finding out that Lacie initially doesn't remember him, Jack doesn't particularly mind because he admires Lacie all the more for how free-spirited she is and how she can't be tied down by anything.
Sukisho: Yoru says to Ran at one point when he fights against his advances. "The more stubborn you are, the more you excite a man's domineering nature."
France of Axis Powers Hetalia groped Italy once and mentioned that "The more you resist the hotter I burn for you."
Though love is not the best way to describe it, Iemitsu from Gate 7, like a good Psychopathic Manchild, loves when he take things he knows he can't have and if they try to run, he likes them more; special mention is Sugihime, a girl he kidnapped for her Seer ability and concideres her "so cute" for always insulting him and wishing him dead.
Kanade Suzutsuki from Mayo Chiki! falls gradually in love with Jiro because of this trope. Where as other guys and girls fawn over her, he's the first guy to overtly stand up to her, although a lot of it is due to her being The Tease towards him till later in the series.
In Date A Live, Miku Izayoi falls in love with Shiorinote actually Shido disguised as a woman, since Miku Does Not Like Men because she is immune to her Compelling Voice. When Shiori says she hates her, Miku says that only makes her want her more.
Jean Grey in the X-Men comics doesn't really seem to earn Wolverine's interest until she shouts him down. Every time she'd telekinetically clobber him and shout "I am no one's property!", it seems to make him hotter for her. Pity every adaptation ever forgets that, having Logan fall for her the instant he first sees her.
The Ultimate Marvel adaptation has this as well. Wolverine underestimates Jean, she blasts him with Telekinesis and afterwards he starts becoming more attracted to her and even abandons his mission to kill Professor Xavier.
The DCU: The latest Clock King is obsessed with Rose Wilson a.k.a. Ravager mostly because she has similar precognitive abilities that can counter his own powers.
ElfQuest: Leetah and Rayek's relationship in the early issues could easily be interpreted this way.
Many Jerk Sue fanfics have the "heroine" as this kind of girl, and guys fall head over heels for her because she treats them "with spunk and feminist will"... in other words, like total crap, which makes her more "interesting" than the other silly, stupid, weaker, girly girls around.
In the Avatar: The Last Airbender fic Sun and Earth, Zuko is put in this position by Toph. She stays in a relationship with him, but has a strong need to stay free. She goes her own way, sometimes appearing in Zuko's life again. He still waits, even being married to Mai, because it's Toph being unreachable that attracts him.
Part of the spark for the Fleur×Harry relationship in the Harry Potter fanfic The Lie I've Lived. Fleur first sees Harry as an actual romantic prospect when, annoyed, he deliberately snubs her in order to ask her close but non-part-Veela friend to the Yule Ball. She is visibly much more satisfied with her relationship with Harry than with her previous ones, which usually involved much older men so strongly affected by her aura that they simply did whatever she told them to.
Very common in Harry Potter fan fiction pairing Draco and an Original Character. Draco is portrayed as The Casanova (often referred to as "the Slytherin Sex-God"), but will quickly fall head-over-heels once it's revealed that the new girl isn't impressed by his pick-up lines.
It's canon that Naruto is pretty rebellious and defiant. In Slash Fic this is sometimes one of the reasons that Sasuke ends up pursuing him.
In the Death Note fanfic ''Feminism'' Fem!Raito gets even more interested in L when her attempts to seduce him (so she can win as Kira) don't work, and in fact he's noticed many for what they were. It's very interesting how in chapter 1-2 she notes herself as far out of his league, when by the fourth or so she admits she finds him attractive too—but still wants to win. It's done very well and over time.
One of the reasons Gaston falls for Belle is because Belle's the only girl in town who isn't taken in by him. Gaston states outright that his interest comes simply from the fact that Belle is the most beautiful girl in the village.
The Beast also starts to warm up to Belle after she refuses to obey and defer to him. Unlike with Gaston, who views her refusal to submit as a challenge to break her to his will, the Beast is inspired by her behavior to be a better person.
The anime movie Howl's Moving Castle gives a gender-flipped variant. The Witch of Waste enjoys pursing "dashing men" and loves that Howl runs from her. It makes it that much more fun to try to get his heart.
Films — Live-Action
In the Fantastic Four movie, Victor Von Doom's assistant wonders, "Why Sue? You could have any other woman in the world." Victor quickly rejoins, "That's why. Because I could have any other woman."
Inverted in Next, where the main character falls for the love interest because his powers work better on her than anyone else.
Groundhog Day pulls this with the lead character, Phil, who is stuck in a Ground Hog Day Loop and can't get out. At one point he uses this to take advantage and convince a variety of beautiful women he loves them or he knew them by learning stuff about them, coming back the next day, and using this knowledge to seduce them. Since every day at 6 when he wakes up everything is reset, he can profess his love to a woman, sleep with her, and wake up without her ever realizing this had happened since technically it never did. This goes well for Phil with everyone he wants except Rita, his producer, whom he spends multiple weeks learning everything about her, and yet not one time does she sleep with him, actually they all end with him being slapped for his behavior. As would be expected, this is the one he falls for.
This is eventually the motivation by which Courtney Thane is shown to be in love with Alix Crown in Quills Window: Her aloof, diffident nature is a stark contrast to any other woman he's met.
Possibly the only reason for Scarlet O'Hara's obsession with Ashley Wilkes in Gone with the Wind is that he is not affected by her "powers of seduction"... at least, not enough to leave his wife.
Elizabeth: Now be sincere; did you admire me for my impertinence? Darcy: For the liveliness of your mind, I did. Elizabeth: You may as well call it impertinence at once. It was very little less. The fact is, that you were sick of civility, of deference, of officious attention. You were disgusted with the women who were always speaking, and looking, and thinking for your approbation alone. I roused, and interested you, because I was so unlike them. Had you not been really amiable, you would have hated me for it; but in spite of the pains you took to disguise yourself, your feelings were always noble and just; and in your heart, you thoroughly despised the persons who so assiduously courted you.
Interestingly, Jane Austen takes the opposite approach to the trope in her next novel Mansfield Park, where Henry Crawford and his sister are both fully aware that the only reason he wants to make Fanny Price fall in love with him is because she's the first girl who doesn't fawn over him and crave his attention. The difference from P&P is that It's All About Me in Crawford's case.
Gender flipped in Austen's Emma, where Emma falls in love with Mr. Knightley, the only person on Earth who doesn't worship her or treat her like she's perfect.
Captain Luthar first falls for Ardee West in The First Law because she's the first woman he's ever met who's honest about her low opinion of him.
Twilight has a variation: "I love you because I can't read your mind." He actually can, and regularly does, control her. Also, it's implied that it's supposed to be because Bella is way too good to fall for looks alone... except that's all she talks about when she describes Edward, so the meaning is lost.
Ciaphas Cain: Probably applies in Ciaphas' relationship with Amberley.
Averted in The Vampire Diaries. Elena notes that Meredith is the only female who seems immune to Damon's charisma, but this only serves to make Damon rather wary of her.
"Face" Loran invokes this trope in the X-Wing Series with Dia Passik, who because of her tough childhood never saw any of his films, and thus is just about the only woman of her age who doesn't gush over him. Although he meant it ironically, in the end the two of them do get together.
Caine for Diana in Gone. He fell for her because she was the only girl who hadn't fallen for his charms.
In The Wizard Heir by Cinda Williams Chima, protagonist Seph has always been able to get any girl he wants thanks to his magically-aided charisma. Then he meets Madison Moss, whose Anti-Magic makes her immune. You can guess where this is going.
In The Novels Of The Jaran, Ilya fall in love with Tess because she constantly defies him when nearly everyone else in the Jaran obeys him. The fact that she doesn't fall for his charisma and good looks like most other women probably factored in, too.
Sophie from Howl's Moving Castle (the book) is Genre Savvy enough to recognize that Miss Angorian, who is not only capable of resisting Howl's charm and is engaged to another man but also smart, pretty, down-to-earth and confident, will steal Howl's heart after witnessing their first meeting but it was Sophie who actually made Howl fall in love with her in the end.
In the novel (and its TV version, True Blood), this is the reason Sookie was first attracted to Bill: She realized she couldn't hear his thoughts.
It's implied that Eric and Sookie's relationship has elements of this. She can't read his mind, he can't glamour her or make her quit her job and live safely as an odd type of housewife. This has nothing to do with the challenge and everything to do with the fact that hearing a guy's thoughts tends to really screw things up for Sookie, e.g. unflattering commentary on her body.
In Trudi Canavan's The Ambassador's Mission Achati laments his control over his slaves — "Only when the person could easily leave you do you appriciate it when he stays" — and seems to have taken an interest in Dannyl at least partly due to a more equal status.
Cassandra, the Physical God antagonist of Full Tilt, has been preying on people's fears for at least several thousand years, but she's never once felt fear herself. The protagonist initially drew her attention by being the sole survivor when she sent a school bus careening off a cliff, but when she challenges him individually, she's both unnerved and strangely turned on by his lack of any apparent weakness for her to target. At various points, she flirts with him, taunts him, offers him a job, and begs him for mercy. (Only that third one seriously interests him, and not for very long.)
In Harry Potter, Harry becomes romantically interested in Ginny after she backs off, makes her crush on him less obvious, and interacts with him in a platonic and friendly manner. In this case, it's less that Harry enjoys the challenge of pursuing her, and more that he finds it unnerving and smothering when girls try to get him to love them.
A non-romantic version of this is apparently a big cause of Breeze's friendship with Clubs in ((Mistborn''. As a Smoker, Clubs is immune to Breeze's Allomancy, and he is immune to more mundane methods of emotional manipulation because everything makes him grumpy.
In The Finishing School Series future duke Felix ignores the girls that throw themselves at him and only has eyes for the protagonist Sophronia who finds him arrogant and is far more focused on excelling at her espionage training than catching a rich, titled husband.
The titular protagonist of Fire falls in love with Prince Brigan partially because he is one of the very few people who has a strong enough mind to resist the mind-altering effects of her inhuman beauty.
There's an episode where Lwaxana Troi is fascinated by someone she cannot read. He turns out to be a hologram, which she is quite embarrassed by.
Similarly, the telepath from the episode "Tin Man" spends a lot of time with Data, whose mind he cannot read. The difference here is that, unlike Lwaxana, he can't not read minds, while Lwaxana just has almost no sense of personal space in that regard. He loves having to discover who Data is as a person rather than being thrust with all that information at once.
In Dark Angel, there is an episode focused on one of the X series fugitives who has Mind Control powers. She's dating this mob guy called Dougie, despite him being below average in pretty much every respect, because her powers don't work on him. She helped him rip off his organisation, manipulating him in more traditional ways.
Sookie was initially attracted to Bill the vampire mainly because she couldn't read his mind, though this was mostly since she wasn't Squicked out by what he thought about her sexually. The fact that he saved her from the Rattrays and fed her his blood, causing her to have sexy dreams about him didn't hurt any. Of course it turned out he'd orchestrated the whole thing specifically to get this response, which may make this a subversion.
There's also Eric, who is mostly into Sookie because he's a bit intimidated by her powers, as shown in a fantasy of his where she tops the hell out of him. Both vampires also feel this way towards Sookie because she can't be glamoured.
There's a bit of this in Castle; Richard Castle can charm any lady he likes around his little finger except for Detective Kate Beckett, who isn't suckered in by any of his usual methods... which makes Castle, who was getting bored with the fawning ladies themselves trying to snare or drape themselves over him, a lot more interested in her as a result. It's also suggested (including by the actors) that it's not so much about Castle trying to find some way to control Beckett as he is kind of thrilled to find someone who can control him, as Castle has no real authority figure in his life except for her.
Scrubs: Dr. Cox loves Jordan because she's one of the only people who can stand up to him. Jordan loves Dr. Cox because he's one of the only people who can stand up to her.
Gossip Girl: Blair loves Chuck because he's the only person who is a Worthy Opponent, Chuck loves Blair because she's the only one who ever seriously challenges him.
Subverted in the Smallville episode, "Heat". When Desiree finds that her seduction power has no effect on Clark Kent, she gets pissed and immediately starts trying to ruin his life. For example, she frames him for arson.
Noah's Arc: This is one of the things that draws Ricky towards Junito early on (as Ricky's sexual advances don't seem to take).
Firefly: Fans would have us believe that Jayne feels this way about Axe Crazy River Tam.
The Secret Life of the American Teenager has this in the pilot, proving that at least one of the writers actually knows how to write. The main love interest, after talking to the main character, talks to his councilor.
"I asked her out, and she turned me down. Of course, I must have her."
Is the "seduction expert" character in Psych, season 5, in love with his friend merely because she's immune to his tactics, or did he fall in love with her because he discovered other things about her due to the failure of these tactics?
Prince Arthur from Merlin begins to fall in love with Guinevere because she's the only one who refuses to suck up to him, and calls him out on his rude behavior.
not true. Morgana called him out on his rudeness and arrogance right from the start, as did Merlin.G Wen was the last of the three other leads to do this.
In Haven, Chris Brody is attracted to Audrey only because she doesn't fall for him like all the town's people do due to his Trouble.
Probably part of the reason why Big BadKlaus harbors a strong attraction for Caroline in The Vampire Diaries. It's part of the reason why he admires her so much at least, which is saying a lot as the guy is very easy to disappoint and can be quick to disown people.
In Sherlock, Irene's first meeting with the protagonist starts with her trying — and failing — to manipulate him the way she would most men (and a statistically significant portion of women). Given that this version of her is all about control, the trope is in play — though she does eventually find a way to dupe him: don't appeal to his sexual desires; appeal to his intellect.
Unlike in the novel, played straight between Damon and Elena literally because her vervain necklace prevents her from being compelled. At least, while she is actually wearing it.
Subverted when Elena gets turned into a vampire with Damon's blood. For the first couple of episodes, Damon says jump, and she says how high, to the point that he convinces her that she can't feed unless she drinks from the vein, and tells her to shut her humanity off. Bonus points for Damon not even knowing he could control her initially.
Don McLean's Everybody Loves Me Baby is a great example of this. "Everybody loves me, baby — what's the matter with you?"
"Crave You" by Flight Facilities revolves around this idea, too. "Why can't you want me like the other boys do?"
I've got guys waiting in a line For me to play my evil girly games With all their minds Just watch me I've got it down to a simple art Just bat my eyes like this And there's a broken heart
But somehow you turned the tables what the hell? I can charm the pants off anyone else but you...
The Rolling Stones' "Ruby Tuesday" is all about this, a woman who lives only for the present ("yesterday don't matter if it's gone"), never stays in one place for long, and can't really be obtained by anyone.
Kat: Why would you care if I never woke up again? Patrick: Because then I'd have to start taking out girls who actually liked me. Kat: Like you could find any. Patrick: Now see, right there, who needs affection when you have blind hatred?
The inverse is also true for the movie — Patrick grows to love Kat because she's not afraid of or especially impressed by him, unlike most of the student body.
In My Fair Lady, Prof. Higgins realizes his attraction to Eliza only when she leaves him and declares that she doesn't need him.
Mrs Lovett to Sweeney Todd. She's consistently portrayed as being very attractive. Preskett Prest, author of the original book, in particular waxes lyrical about how captivating she is to the men that visit her shop and most adaptations go with that and make her very flirty) but Sweeney is largely immune to her charms, or incapable of having a real relationship with her. Or else he mercilessly uses her as a pawn in his plotting...
Tales of Symphonia: Zelos Wilder is used to girls throwing themselves at him, so naturally he takes a keen interest in Sheena, who refuses to fall for any of his charms. If you get Zelos's backstory, he reveals that his happy-go-lucky exterior is just a facade, and he's actually quite cynical—and that especially goes for his instant harem, whom he believes is more interested in being with Zelos the Chosen than they are in Zelos the person. Sheena doesn't care if he's the Chosen or no, meaning that whatever she is feeling for Zelos — even though it's currently "he's a disgusting pervert" — is genuine.
In Dragon Age: Origins, due to her Social Darwinist approach, Morrigan is frequently left exasperated by the actions of a heroic Male Warden. Particulary after she realises that she's actually started to develop genuine feelings for them.
Gilgamesh towards Saber in Fate/stay night. In one route he even states to her face as he's dying that "Some things are more beautiful because you can't have them." In one of the alternate timelines in a sequel game he's actually disappointed when he sees that Dark Saber has abandoned her ideals and become corrupted.
Togainu no Chi: Shiki is interested in Akira because he refuses to surrender to him and doesn't beg for his life.
In Nicole, the best way into Jeff's heart is to challenge him and/or go outside of his expectations. For someone who bases his entire persona on what he expects that people want to see, he's intrigued by Nicole when she does the opposite of what she "should" have done.
Gunnerkrigg Court: Not love per se, since he seems incapable of loving anyone besides himself, but Coyote is clearly fascinated with Antimony and Reynardine precisely because they're not afraid to disagree with him or brush him off. In contrast, Ysengrin is a fawning yes-man to Coyote, so Coyote barely gives him the time of day. Except of course when he's eating Ysengrin's memories.
Skin Horse: Tigerlily Jones is the only (human) female to appear for more than a panel and not find Tip extremely attractive. She barely even noticed him unless forced to. This is probably the main reason she's the only woman Tip's actually thought twice about (without sleeping with her or her trying to kill him).
In The Weekenders, Carver tries to set Tino up with a popular, stuck-up girl; the girl isn't interested in Tino, until she discovers that Tino isn't interested in her either. Then, she becomes infatuated with him, claiming that "unattainable boys are so fascinating".