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Anime and Manga
- C.C. in Code Geass is seen as this In-Universe. Her role is somewhat muddled by the fact that while she is directly behind Zero's actions, none of the Black Knights actually know what her real role is, and assume she's Zero's mistress. Zero doesn't care, but C.C. at least attempts to correct Tamaki about this, though he doesn't believe her. In reality, she doesn't really fit this trope, having a definite character and ulterior motives beyond helping Lelouch.
- Misa Amane from Death Note would be a clearer example. Light definitely isn't a Hero. Then again its debatable whether or not she actually counts as his girlfriend.
- One Piece: Depending on your subber or dub, Nico Robin is either explicitly or implied to be Crocodile's bedroom buddy. Considering she still acts similarly, and she seemed far from that close with any of the Straw Hat crew (Until the Enies Lobby arc, at least), it seems like it's more of an act she learned to put on without actually having any meaning.
- Gyokumen Koushu from Saiyuki is the diabolical mistress of the human devouring Gyu-Maoh. Also posing as a main villain throughout the plot for attempts to revive him and bring him back to power.
- Kanae from Revolutionary Girl Utena. Heavily deconstructed: her parents barely cares about her and her mom cavorts with her fiance, it's clear that Akio is only engaged to her to gain control of Ohtori, she's shown as incredibly nervous about their relationship and her dealings with his very odd younger sister Anthy, she cracks BADLY once given enough prodding by Mikage and Mamiya, and ultimately it's implied that Akio and Anthy are slowly poisoning her.
- Princess Charlotte from Berserk is head over heels in love with Griffith, who turns into the series Big Bad in an EPIC WAY. Yet she still remains in the dark about all of the horrific actions he has done as well as his true nature. While she's not a big plot device in the story, Charlotte is still of importance to Griffith - not so much as a love interest, but as a Meal Ticket to the throne of Midland. And holy shit, does the story break her.
- Kriem is this for Jake Martinez in Tiger & Bunny. She believes in his cause (that is, NEXT supremacy) and has a power that allows her to help him actively. Bonus points for having a similar visual motif to Harley Quinn.
- Harley Quinn from Batman is in an abusive relationship with the Joker. It's a connection she can never quite shake off even when Poison Ivy shows her she can be a supervillain without him, and Batman shows her she doesn't have to be a supervillain at all. In fact, it seems that every time Harley isn't Joker's Dark Mistress, she's Ivy's. In the DCAU it's only after Joker dies that she's finally able to get out of it.
- In Captain America, there was the relationship between Mother Night and the Red Skull. The Skull being who he is, was horribly abusive to her even though she was completely loyal to him.
- Thanos's love interest is the Anthropomorphic Personification of Death, though she isn't a villain.
- Miss Tessmacher and Kitty Kowalski from the Superman movies.
- To Lex Luthor, not each other.
- Viper from Doomsday, her death making Sol even more Ax-Crazy.
- Mirage from The Incredibles. Does a Heel–Face Turn.
- In G.I. Joe: The Rise of Cobra it's clear Destro wants or even sees The Baroness as this, but she's having none of it.
- Vulnavia in the Doctor Phibes movies. Although Phibes (Vincent Price) isn't really in love with her (he's pining for his dead wife), she clearly fills this role.
- In Madhouse, film star Paul Toombes (Vincent Price) plays a character named Dr. Death. Paul is annoyed when the producer insists on giving Dr. Death a pretty assistant, and even more annoyed at how unprofessional the actress (who happens to be sleeping with producer) is.
- In The Big Heat, The Dragon's girlfriend starts out as the ditzy type, ignoring her boyfriend's vicious tendencies. Until he turns on her, that is.
- Cara Carozza from Dr. Mabuse, the Gambler , but she isn't just a mistress for eponymous Dr. Mabuse, but also is his henchwoman, and resident vamp.
- Bellatrix Lestrange from Harry Potter very clearly wishes she was Voldemort's mistress, but Voldemort really doesn't have time for that kind of nonsense. Bellatrix is married, with her husband being mentioned only briefly and the movies cutting him out entirely, but she probably wouldn't mind cheating on him, being evil and all, especially since Word of God is that it's a loveless marriage.
- Irma in Bulldog Drummond is probably this, although she doesn't seem to actually do anything except lounge about on the villain's sofa being glamorous.
- Left Behind: When Hattie Durham is introduced to Big Bad Carpathia, she's extremely enamored of him. She kind of sours on him when he has her put in a women's prison after she gets pregnant (with his child).
Live Action TV
- In Doctor Who, Lucy Saxon is an unusual example. She's not just The Master's companion and girlfriend. She's his wife. She insists that she's to stand by him for better or for worse at first, even though he's evil. Later, their relationship becomes more empty. Eventually it becomes clear that the Master doesn't care about her, and even becomes emotionally, physically, and even (it is strongly implied) sexually abusive. By the end, she's well past blind, doe-eyed admiration. In fact, sometimes it seems she loathes him for how he's broken her spirit. So it's not suprising when she fatally shoots him, while giving a vacant look.
- Heroes featured Danko's mistress, who didn't seem to know but who broke it off with him when she found out what a complete psycho he is.
- Harmony in Buffy the Vampire Slayer took a turn as this after becoming a vampire, dating Spike. She was pretty much The Load to his group, and she eventually broke up with him for treating her as an annoying nuisance, but got back together with him several times. Her attempts to go solo as a villain were feeble enough that she eventually got an office job instead.
- Stefan and Damon were the male versions of this for Katherine when they were human in The Vampire Diaries
- Reverend Steve Newlin becomes this to Evil Overlord Russell Edgington in Season 5 of True Blood
- Gender Flipped on Merlin, in which Morgana was calling the shots, and Agravaine was her thoroughly whipped gofer.
- Polly Peachum in The Threepenny Opera. Interestingly, she's the main character, and spends much of the play (and the novel) wondering how she got into this situation. It's essentially Marxist commentary on the inability of young women to realize they can live independently of men, and to realize that there's other ways of being financially secure than (a) a criminal life or (b) a life as a sex object. (Later on in the play, Lucy is a straighter example of the trope. She's replaced by Fanny in the novel.)
- Sarevok in Baldur's Gate has Tamoko, who shows up as the penultimate battle in the game. She can be talked out of it, but canonically she dies during the fight.
- A very rare gender-flipped version of the trope is seen in Final Fantasy VIII: Seifer's entire goal in life is to be a sorceress' Knight (protector/henchman/plaything). He ends up being lured in by the villainness almost instantly, being reduced to her lackey for the rest of the plot. Whether or not there's a sexual element to it is left unexplored. Said sorceress is also his foster mother. Or so it seems.
- Both Overlord games play this trope very straight, with the evil player character getting the chance to actually choose between several mistresses who pledge themselves to you, ranging from relatively normal women with inexplicable crushes on you, to extremely narcissistic yet beautiful women who enjoy the power and attention.
- Fire Emblem
- In Radiant Dawn, Almedha is revealed as the Dark Mistress to the deceased Big Bad of Path of Radiance, Ashnard. Fits perfectly in that they were never married, though really she wasn't "together" with him long, as after their child was born and she lost her powers, he claimed to hold that child hostage to keep her contained, despite the fact that he dumped the child as an orphan long ago. Her son's identity factors heavily into the plot.
- Princess Ishtar of the Jugdral series. As the fiancee of the evil Prince Julius, she fights the protagonists despite a case of My Lover Right or Wrong and partially knowing Julius, despite caring for her in his yandere ways, is using her.
- Borderlands 2 has Nisha, the girlfriend of Handsome Jack and a tyrant who rules Lynchwood with an iron fist.
- BioshockInfinite: Lady Comstock, at first. She took on a new philosophy based on Comstock's religion, where sins are basically raw divinity and must be tempered into virtues. Despite her insane husband planning a campaign of city-razing. It took a while, but eventually the hypocrisy got to her and she called her husband out; BIG mistake.
- Tales of the Abyss plays this straight in one case and subverts it in another. The straight example is a teenage version in the game's backstory, where the original Ion had Arietta. She was utterly devoted to him, even though he was a Nietzsche Wannabe with a complete Lack of Empathy. The subversion is in the main game, where it seems like Legretta is this (specifically the Lady Macbeth kind, since she truly believes in her love's ideals and does whatever she can to further them) but the Big Bad is Oblivious to Love.
- Excella Gionne, from Resident Evil 5. The CEO of a major multinational corporation, she is a valid threat in her own right and overlaps with The Baroness. Unfortunately for her, she made the mistake of attaching herself to Wesker and believes that they will rule the world together. The moment she's no longer useful to him, he deals with her in his usual fashion.
- In the Whateley Universe, Gizmatic's wife, the mother of Jobe Wilkins. Whenever Jobe meets a particularly ditzy girl, he may tell her she reminds him of his mother.
- Although prominent in many Batman comics today, it was in Batman: The Animated Series that Harley Quinn was introduced as Joker's girlfriend/henchman in an abusive relationship.
- Doctor Girlfriend from The Venture Bros. is a supervillain in her own right, but because she doesn't have any gimmick to theme herself around, she wear a ritzy Jackie Kennedy wardrobe and defines her acts of villainy in relation to her romantic partner, The Monarch. Toward the end of the first season, she dumps him for Phantom Limb, and we see how ineffectual The Monarch is without Doctor Girlfriend around as the voice of reason. Dr. Girlfriend doesn't fare much better either, as Phantom Limb reminds her of why she left him in the first place: Limb is a high-class bore who simply wishes to have her prance around his mansion in skimpy outfits, as opposed to the Monarch, who treasures her intelligence as well as her being "heat incarnate". With the Monarch, she's second-in-command; with Phantom Limb, she serves drinks to house guests.
- On Gargoyles, Fox starts out as this to Xanatos, but their relationship quickly evolves into more of an Unholy Matrimony. Their love for each other (and eventually their new baby, Alexander) is a major aspect of their eventual Heel Face Half Turn into an Anti-Villain couple.
- Perhaps meant to be parodied on Phineas and Ferb, where Mad Scientist Dr. Doofenshmirtz tries to get a girlfriend, but it never works out, even when he once met a girl as evil as he is. He's also divorced with a child, though his ex-wife apparently never found out what he did for a living.
- The Fairly Oddparents: Anti-Cosmo has Anti-Wanda. It's a slight variation, as the two are explicitly married.
- In Spongebob Squarepants, Plankton has a computerized wife named Karen, who serves primarily as a voice of sense he never listens to.
- Averted in Avatar: The Last Airbender. Azula may be a brilliant chessmaster and a highly skilled Manipulative Bitch, but she is too unfamiliar with everyday social skills to form a relationship, so much that the one guy who could have been closer to her was driven away by her loud declaration of We Can Rule Together.
- Toyed with in the relationship between Zuko and Mai though. He's former main antagonist (on the cusp of a Heel–Face Turn), and she's the Dark Action Girl who came along on the villainous ride because she was bored and had nothing else to do. In the end though, she is one of the few positive things Zuko has to turn his back on when he leaves the Fire Nation. They even share a cheesy scene where they both agree how they hate just about everything...except each other.
- Captain Planet and the Planeteers has a Gender Flipped example, sort of—female Mad Scientist Dr. Blight, whose seems to be positively flirting with her computerized Dragon, MAL, in many episodes. (They often call each other "MAL baby" and "Doctor Dearest"...)
- The Legend of Korra:
- The Red Lotus is led by Zaheer, while P'Li is his girlfriend. The two clearly care about each other, especially since her death was enough to eliminate his last earthly tether and activate his ability to fly.
- Gender Flipped in the final season: Kuvira is the Big Bad, while Bataar Jr. is her fiancé and devoted second-in-command.