You know the difference between a slut and a bitch? A slut will screw anyone. A bitch will screw anyone but you.
So there's this one girl. You know the one. The one who Really Gets Around. She'll jump into bed with just about anyone who asks. She...well, she just really likes having the sex. You get the point.
But this girl, who will schtupmen, womenand most species of plants, is utterly unobtainable for this one character. That character doesn't have to be the protagonist, and, in fact, rarely is. Most of the time this is used to demonstrate that the character's sad and pathetic; after all, if Betty Bangs-A-Lot won't kiss him, he must be pretty crummy at this life thing. This is almost always used as a comedy gag, largely because it's too depressing to contemplate under any other circumstances. Think of it as Even Sluttiness Has Standards.
More rarely, on the other hand, it can be used to demonstrate quite the opposite. Sometimes the reason the promiscuous character refuses to have their usual mindless, consequence-free sexytimes with one target is that just this once, they're holding out for something more meaningful.
Note that pronoun-laced description aside, this trope works perfectly well with Manwhores.
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Anime & Manga
In Panty & Stocking with Garterbelt, Panty has sex with nearly everyone but Brief. She did offer him sex once, but Brief thought it was going too fast. Panty dropped the option right then. She does try and do it with him once she finds out that he's Beautiful All Along, but by then her hymen's rebuilt and damn-near impenetrable. They finally do the deed in the last episode, which restores her powers.
In Neil Gaiman's 2006 relaunch of "The Eternals", Sprite, while explaining that his motives boil down to being really sick of being stuck in a prepubescent body, notes that he's the only male Eternal with whom Sersi hasn't slept.
The EvangelionH-fanficThe A.L.I.A.S. Vignettes has Asuka finding a really creative way to torture Shinji: whenever she has a date, she drags the poor shmuck back home, throws Shinji out of his room then does the deed in there, knowing full well that Shinji is within earshot. And she's not doing this because she's a slut, she's doing this purely out of sadism.
A major plot point of theNarutofanficThat Look, in which Anko sleeps with everyone in Konoha but Naruto, and even reacts violently whenever he so much as touches her... After she gets him drunk and climbs naked into bed with him. And she seems to believe that he's in the wrong when he disapproves of her actions.
In the movie Innerspace, nebbish hero Jack Putter's dysfunctional love interest Wendy idly remarks on the irony of her sleeping with just about everyone he knows except him when he's the one guy she might actually like. At the end, after he's taken a level in badass and she tentatively suggests they start dating ("Jack, I think we should try dating. Maybe not exclusively at first, at least for me, but... "), he brushes her aside with a quick "not a chance" before moving on to his next adventure.
In Trucker, Runner calls Diane out on this fact, although her reason for not sleeping with him is a pretty damn good one considering he's married, but his frustration comes from her blatant refusal to acknowledge the fact that they have a thing for each other, not simply because she won't sleep with him.
In Jingle All the Way, Sinbad's character, a mailman, complains about having to pay alimony to his ex-wife, who slept with everyone at the post office except for him.
In Dangerous Beauty, courtesan Veronica Franco sleeps with a very high percentage of the Venetian aristocracy, but refuses Maffio Venier, since he cannot afford her. He resents this, which becomes very important to the plot later.
A Song of Ice and Fire: A side character (whose face is covered with boils) reminisces about his boyhood in a small village. As a teenager, he spent hours gathering flowers for a girl in the village who had the "town slut" reputation. When he presented them to her, she laughed at him. So he killed her.
In Use of Weapons, Diziet Sma, The Handler, is definitely a Good Bad Girl (which makes sense, since the Culture is the epitome of Fetish-Fuel Future). That being said, the one person she won't sleep with is the novel's other protagonist, the sociopathic badass Zakalawe. It's hard to tell if this is because she wants to keep the relationship professional or is somewhat turned off by him. But it's not for lack of trying on his part.
This is part of what drives the protagonist of The Player of Games so nuts that he embarks on the epic journey that constitutes the plot. It should be noted that this is in the Culture, which is ridiculously sexually liberated (the hero is widely considered a bit odd because he has never changed sex!), which makes the snub even more annoying than usual. She does at least give him her reason when he asks, and he has trouble denying it; she gets the feeling that he's such an obsessive gamer that he treats their relationship like one, and thinks of her more as a piece to be taken than as a person he wants to have sex with.
There's a short by Fukazawa Shichiro with this premise. The main character is a Jinmu ( a derogative term for second born son), in a village where second born are treated like livestock (they aren't even allowed to heve sex, ever). One man who feels guilty for killing a Jinmu once, leaves a will behind before dying declaring that his wife must sleep with every Jinmu in the village. Guess who's the only one left out.
In the novel Super Folks, David Brinkley's ex-crush is known to have slept with every superhero except him. In this case, however, it wasn't because of any sort of disgust (indeed, it's implied she would have, if he'd tried) so much as him never thinking to go for it.
Penny from The Big Bang Theory has slept with dozens of men, including Leonard and Raj (the former while drunk), and even Sheldon has at least seen her naked. Even she, however, refuses to sleep with Howard, who fancies himself a casanova.
Penny: I know you think you're some sort of smooth-talking ladies' man, but the truth is, you are just pathetic and creepy.
Howard: Um, so what are you saying?
Penny: I am saying it is not a compliment to call me doable. It's not sexy to stare at my ass and say, "Ooh, it must be jelly 'cause jam don't shake like that." And most important, we are not dancing a tango, we're not to'ing and fro'ing. Nothing is ever going to happen between us EVER!
Howard:Wait a minute. This isn't flirting, you're serious!
Penny:Flirting? You think I'm flirting with you? I am not flirting with you, no woman is ever gonna flirt with you, you're just gonna grow old and die alone.
In Lexx, Zev/Xev is a love slave with an unslakeable libido - but she refuses to have anything whatsoever to do with Stanley, whom she sees as repugnant. Ironically, she herself fails to bang anyone, since her choice of lovers tend to be killed, are already dead, is a disembodied robot head, or is Stanley.
Stuart in the British version of Queer as Folk will sleep with anyone (once) except Vince. Vince's mother says it's because Stuart's "saving him" for when they're both old. They do eventually settle down with each other, but it takes the run of the show to get them there.
Happens in the US version as well. Though Michael gets over Brian eventually, and they both settle down with other people.
Jadzia Dax on Star Trek: Deep Space Nine had a love for men of all species (and even a woman in one episode) but would not sleep with Dr. Julian Bashir, who had a huge crush on her.
May or may not be subverted after the Dax symbiont is implanted into Ezri. A lot depends on whether it was the Dax symbiont or just Jadzia that wasn't interested in Bashir.
Gina from The George Lopez Show will sleep with Anything That Moves...anything, that is, that can get past the initial nausea. At one point, Ernie decides he's finally gotten desperate enough to make a pass at her, which she turns down.
Gina: I guess I have standards. Hey, I'm as surprised as you!
Male example in Owen of Torchwood. He sleeps around quite a bit, even having affairs with two of his coworkers (one of whom was in a relationship at the time), but never even notices Tosh who is madly in love with him. He even calls her on it in "A Day in the Death."
Owen: For some reason you want me. You know I don't know why, but you always have — always looking at me, watching me screw all those other women, your heart breaking.
Subverted on Frasier. Roz gets all over every man as soon as she sets eyes on him, but doesn't get with Frasier. However, both of them know this is because they don't want to hurt each other's friendship. In fact, when she finally does have a fling with him, both of them panic about it the next day.
This is explored in one episode when Rox starts a relationship with a psychiatrist who mentored Frasier through college and who is similar to him in many ways, prompting Frasier to be uncomfortable around him after he inadvertently catches them together at her apartment one night. He comes to realise that he's actually sublimating his jealousy about this trope (although she gets tetchy when he initially tries to phrase it in these terms), since he'd previously been able to comfortably rationalise the situation with the assumption that he simply wasn't her type but has now received confirmation that he could be.
Roz: Frasier, did you ever stop to think there may be something special about not being picked? Frasier: Roz, that didn't work when I was cut from pee-wee football, it's not gonna work now.
Laurie from That '70s Show, after marrying Fez, refuses to sleep with him. She'll sleep with everyone else during this time and he calls her out on it. Ironically enough she did sleep with him once and only once, before they married.
In the first season of True Blood, Jason Stackhouse will pretty much bang anything female... except Tara, who has a huge crush on him. Of course, considering what happens to the rest of his conquests, that may not be a bad thing for Tara.
It might be more that Tara's his sister's best friend and they grew up together; it would feel like bedding Sookie.
A victim on an episode of Psych would have sex with everyone but the killer, who was more or less a Stalker with a Crush , resulting in said murder.
Mythology & Folklore
Classical Mythology (and all variations thereof) gives us the Aphrodite who was widely known for bedding gods/mortals/anything with a penis EXCEPT her husband Hephaestus. Zeus dodges this by taking the "Sleeps with Everyone AND You" approach when it came to Hera (though it didn't help much in Hera's eyes).
Chris Jericho cut numerous promos regarding Stephanie McMahon being a slut, one promo suggesting that she had slept with "three quarters of the locker room, and the lighting crew, and the camera crew, and the sound technicians, and the stage hands, and the prop guys, and the merchandise sellers and Louie the popcorn vendor in the 15th row!", followed with saying she'd slept with everyone on the planet earth, before bringing out members of The Planet Of The Apes. Everyone however, did not include Jericho, leading to some Foe Yay sexual tension.
In Seminar, the only guy Izzy doesn't sleep with (at least during the course of the play) is Douglas. This is rather ironic, first because Izzy is using Douglas for his connections in the literary world, (and you'd think a little action would make that easier) and because Douglas is probably more attractive than the other guys in the play. (And unlike the teacher she sleeps with, isn't old enough to be her father).
In Too Human, Freya (Goddess of Love) rightfully has a reputation for jumping in bed with just about anyone, and indeed goes to some length to lure the main character to her bed (unsuccessfully, but that's mostly because he's too busy trying to avenge his recently-dead wife). The only one who actually calls her out on this, however, is the ever-brash Thor, who refers to her as 'The whore of the Gods', and accuses her of having 'been' with every man in the hall (it was during a council-meeting of the entire Aesir Corporation.) To this, she snarkily replied "Aye, I've been with every man here, but I've not been with YOU. Not that you'd know what to do with me." The hall is leveled with laughter as Thor splutters angrily.
During Act 3 in Dragon Age II, Hawke encounters Emile De Launcet, a disgusting little man who claims to have escaped the Circle so that he can have sex with a woman. Hawke can offer Isabela's services in exchange for his return to the Circle, at which point Isabela refuses, saying that she does have some standards.
Jodie in Loserz has slept with virtually every person her age, of both genders, in the entire zip code. Except for her two best friends, Ben and Eric. Oddly enough, this isn't even used to lampshade how pathetic they must be (although they are both geeks): Even at their horniest and loneliest, even if they're all stoned, neither of them seems to even think of asking Jodie for sex, or vice versa. Its just not in their mental universe at all. All three of them are just that deep in each other's Friend Zone. At least it's mutual.
Faith Abbot from Magick Chicks sleeps with almost entirely everyone… except with her secretary, who happens to have one of the largest crushes on her. The girl isn't pathetic or anything and in fact is a great help to Faith, so one can't help but wonder why she does this.
In the backstory of Shadowgirls, teenaged Charon (pronounced "Sharon") was portrayed as going through every bad boy in Innsmouth, while using her best friend, Jackson, as an emotional backstop when those flings inevitably went sour. When Jackson finally has enough and tells her off, Charon tells him that she would've turned to him... eventually. It's implied that they do actually get together later... just in time for Charon to disappear and return, amnesiac and pregnant.
Elza: That tribe perished, leaving Mifi as the last priestess. That said, she must stay pure, or else her powers will disappear. If she loses her purity, just to satisfy myself, Mifi's tribe will perish in a different meaning. If it wasn't for that, I wouldn't be showing any restraint... Seren: (Why is she a good person under this circumstance?)
Clone High has great fun with this with Cleo's many references to sexual escapades, yet Abe has to jump through several incredibly difficult hoops to get anywhere near sex, even after he becomes her boyfriend.
Titan Maximum: Sasha sleeps with just about everyone. And yet, she finds team nerd Willie utterly repulsive. He worships her and dreams about one day touching "her left, or, even better, right, boob!"
A variant in Metalocalypse. Dethklok, being Dethklok, is besieged with women who will do unspeakable sexual things with every member of the band... except Murderface, the bass guitarist so ugly and unpersonable that being in a band that can raise mythological monsters and change the very nature of reality still isn't enough enough to get him laid.
Not even the female roadies (who are all loyal to the band) will sleep with him.
Family Guy: Seemingly, every teen-aged boy in Quahog will sleep with any teen-aged girl... except Meg Griffin, who is portrayed as so hideously ugly that boys will go out of their way not to have sex with her; several have taken extreme measures to avoid the humiliation of having "scored" with Megan. Usually this is implied, such as the hunk who, after Meg asks him to a dance, kills his own little brother just so he has an excuse to avoid going with her.