"Look, what happened between us was important to me, and I thought it meant something to you too. But clearly Elsa means more to you than I do."
— Alejandra, La Verdad Oculta
Alice and Bob (though gender reversals are common here) have decided that they want to pretend to be a couple to make their exes jealous, or pretend they're Happily Married to make sure Bob isn't deported, or decide that sex doesn't need to have an emotional attachment and become Friends with Benefits.
It all goes along swimmingly, until Bob starts feeling something for Alice. It can start by finding out she and he are very compatible, or as a jealous Green-Eyed Epiphany when she goes off with a boyfriend or has sex with someone else. Eventually, their perfect arrangement starts to fall apart as the ground rules are broken, leading to a confrontation.
Alice may or may not have feelings for Bob, but even if she does she'll defiantly say that their time together "meant nothing to me", to which Bob will plead his love with "It meant something to me, dammit!" This might be substituted with "I felt something!" and "I felt nothing!" Of course, Bob will storm off heartbroken that the woman he loves has just shot him down like a World War One observation balloon.
If Alice really doesn't have feelings for Bob, then it's heartbreak time (happily, Bob will likely come to realize he's been thoroughly neglecting Claire and hook up with her). If she does, she's likely been denying her feelings, something another character will have to spell out to her very plainly before she realizes she loves Bob, and goes after him seeking forgiveness.
Compare Becoming the Mask. May also be stated after asking the question, "Was It All a Lie?"
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Anime and Manga
Pretty much a given in Shoujo romantic drama animes. Especially if there's a Love Triangle or something to that effect.
Flay and Kira in Gundam SEED. Kira did like her, but when their relationship started she was definitely in Yandere mode, so she failed to realize that she did love him until it was too late. By the time she gets her emotional issues sorted out in that department, Kira isn't around and she gets taken prisoner and it just goes downhill from there for her.
Yu-Gi-Oh! has one of these, in an indirect and implicit way in episode 90, when Mai asks Jonouchi/Joey whether she was in the dream he had of all his friends after he's knocked out by a bolt of lightning caused by Odion pretending to be Marik, summoning Ra by using a counterfeit card in episode 89, at which point Joey gets shy/flustered and lies to her.
In Devilman, Ryo gets his memories back, remembering he is Satan betrays Akira and leaves him with an impression that their friendship was just a lie. Not only it isn't true, Ryo is in love with Akira.
In Rurouni Kenshin, Tomoe lost her fiance at the hands of Kenshin, and Kenshin and Tomoe pose as a married couple for a time, but then they actually fall in love, and Kenshin tells her that their marriage needn't only be for show.
In an early episode of Haruhi Suzumiya, Kyon gets Yuki a library card, since that's the only way to get her out of the library and to the meeting with Haruhi in a reasonable timeframe. Kyon thinks nothing of it, and Yuki certainly doesn't make anything of it, but during The Disappearance of Haruhi Suzumiya, when Yuki rewrites the world so that she's a normal human, she is careful to keep that memory.
Possibly the most triumphant example being Vanilla Sky, with Tom Cruise and Cameron Diaz's characters finally hashing it out in a moving car. Cameron Diaz is driving. She's very despondent. It doesn't end well.
Tearfully "I swallowed your cum. That means something!"
Chasing Amy has Holden tell Alyssa that she meant something to him.
Groove has this line:
Ernie: Happens to me at least once every party. Some guy comes up to me and says "Thank you for making this happen... I needed this. This really meant something to me." And they nod... and I nod back.
As does Tangled, the 2001 film.
Alan: [Crying] I loved you! Tell me I meant something to you!
After having sex, the titular characters of Zack and Miri Make a Porno feel something for each other. Zack is the first to admit it, with Miri denying she felt anything because she thought Zack had sex with another actress and didn't reciprocate her feelings... and then Zack leaving, because he thought Miri had had sex with one of the porno's actors. This may be a theme in Kevin Smith's films.
In Life as We Know It, Holly and Messer are forced to live together like husband and wife and raise their goddaughter after her parents die. Of course, they hate each other, but grow to like each other. After it gets too serious, Messer leaves for a job in Phoenix. He comes back for Thanksgiving, after which Holly gets with Sam. Messer admits that he actually loved Holly.
In Stone Of Tears, after one of Richard's teachers (the one closest to him) is revealed as a villain (after trying to drain his gift and life out of him), Richard said that he thought she cared about him... and she answered that maybe she did, and that's why she tried to drain his gift instead of bleeding it out of him - which is normally accomplished by Flaying Alive the person in question.
At the end of The Hunger Gamesthis happens between Peeta and Katniss. She thought their romance was all for the cameras; he truly did love her and thought she had finally begun to reciprocate.
Live Action TV
Cordelia in Angel has this reaction to her co-worker and potential love interest Doyles parting kiss.
Cordelia: Doyle! I thought our kiss meant something. And instead, he-he used that moment to pass [prophetic visions] on to me. Why couldn't it have been mono or herpes?
Cordelia (or maybe not) was later on the other side of this equation with Connor.
This is various played straight, averted, and subverted in layers on Chuck between the title character and his CIA handler Sarah, who pretends to be Chuck's girlfriend as a cover for most of the first two seasons. This trope contributes a central part of the drama of the show.
Chase says this to Cameron in House and she immediately breaks up their "friends with benefits" relationship, claiming that she warned him not to fall in love with her. She did explicitly warn him and she does end up marrying him, at least for at time before she couldn't forgive him for killing a patient on purpose, even if the patient was a terrible dictator. Or rather, she could not come to terms with his having accepted what he did (ie, would NOT undo it given the chance).
Played beautifully straight in a later episode, leading up to them possibly getting back together. But then not (at least they got closure).
Subtle version in Firefly: Mal and Inara dress up and pretend to be a couple to go stake out the villain of the week together at a theater. No big deal is made of this. Mal agrees to help a friend of Inara fight against the villain, one thing leads to another, Inarafinds out.
Mal gets some of this in the next episode, as he's trying to convince himself their relationship doesn't mean anything.
Denise proposed a FWB arrangement with Brad on Boston Legal, which ended when Brad realized he wasn't comfortable with it. When she found out she was pregnant with Brad's baby, she agreed to marry him.
Happens in Ned And Stacy during the series finale on the former's part.
On Will and Grace, it is revealed that an old girlfriend of Leo's, Diane, is the only woman Will ever had sex with. He attempts to comfort a jealous Grace by telling her it meant absolutely nothing and he only did it to verify his gayness, whereupon Diane bursts out that it meant a lot to her and was in fact the only time she'd ever had an orgasm.
Also invoked during Chandler and Monica's Friends with Benefits relationship when Monica is (unwillingly) set up with another guy. Chandler is hurt and claims It Doesn't Mean Anything because they were 'goofying around' but later admits that he cares about her and it isn't just a fling.
On Mad Men Don Draper had sex with Allison, his secretary, during one of his drunken binges and tries to pretend that it never happened. The woman seems to go along with it for a while and then snaps, throws stuff at him and quits.
Allison: this actually happened
On My Name Is Earl, when Joy was still married to Earl (but having an affair with Darnell), a recurring problem in Joy and Darnell's illicit relationship is that it's all about sex. Joy is OK with that (she actually did love Earl and wasn't ready to leave him at that point), but Darnell wants to actually go out on dates and be a real couple. Joy tells him that it's out of the question because she's already married, and the two proceed to argue. She angrily dumps him for a while, but they eventually get back together...and a few years (and a Chocolate Baby) later she finally leaves Earl for Darnell.
Avril Lavigne's 'Losing Grip'. It...sounds less clunky in context.
Are you aware of what you make me feel, baby?
Given an interesting twist in Ace Attorney: Trials and Tribulations. Obviously Phoenix meant nothing to Dahlia... but all the emotion moments Phoenix had with Dahlia were really with her substituted twin sister Iris. And to Iris, Phoenix did mean something.
Played with in Questionable Content. Sven and Faye are halfway into Slap-Slap-Kiss territory when they start up a friends with benefits setup until Sven screws it up by sleeping with another girl. After it falls apart, they both realize that it meant something to them. Faye eventually forgives Sven, but they don't continue their relationship.
A non-romantic version can be found in Tower of God: Ho asks Baam if he really thought that they were friends just because of a signature on a friendship list. He did.