"My thoughts ran to Rousseau and Swinburne, both masochists, both geniuses, suffering their mistresses' cruel lashes even as they cried out for perfect enlightenment. Perhaps the body is not our being's basest part after all. Perhaps it is the royal road to knowledge."
— Presley Abbott, The Oxford Girl
In fiction, people who enjoy BDSM have a tendency to be intellectuals. Possibly because BDSM tends to be more about the psychological mind games than just the ropes and spankings.note This correlation may have some truth, one survey found 20% of practitioners have post-graduate education. In a similar vein, coming up with creative ways to employ the various paraphernalia involved can be attractive to those with a technical or mechanical bent i.e. The Engineer. Thus, an interest in BDSM can be used to underscore the character's intellectual side - making this trope a mostly "positive stereotype" likely to be used on protagonists and other sympathetic characters.
However, it can also be used as a way to establish a villain as Wicked Cultured. This easily drifts into the Bondage Is Bad kind of Unfortunate Implications, unless counterexamples are provided or the Safe, Sane and Consensual trope comes into play.
In some works, Brains And Bondage will take the form of waxing poetic about pain, submission and/or power psychology. In some Anti Intellectual works, it will instead be used as a blunt tool to make intellectuals look bad by invoking prejudice to make them seem "abnormal".
See also Casual Kink. Contrast with Bondage Is Bad, which is the portrayal of bondage and bondage-themed characters in a negative light.
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Anime & Manga
Nana of Nana to Kaoru is an ace - she's on the student council, athletic, beautiful and a top student. When Kaoru's mother confiscates his bondage stuff and hands it to her for safekeeping — well, we won't spoil it. Suffice to say she finds that bondage clears her head like nothing else because she can step outside what everyone thinks she should be, and as a result her grades go up. Brains + bondage = More brains?
And Tachibana, the sex shop owner and personal slave to Kaoru's favorite author, went to graduate school at Todai, the most prestigious university in Japan.
Ruby is The Smart Guy of the Newspaper Club, has extensive knowledge of various monsters and forms of magic, is a capable strategist, works as the direct assistant to the school's board chairman, and is a blatant masochist who compares tying herself up BDSM-style to winding the phone cord around your finger when you're bored.
Kagome Ririko, the math teacher of Yokai Academy, dresses up like a dominatrix during private tutoring.
At one point, it's casually mentioned that the Riddler's female henchmen (henchwomen?) used to work in a BDSM club.
In Lucifer, the character Lady Lys tends toward philosophical musing when it comes to pain.
For the record, she is a demon and pain harvested from human souls and refined into a powder-like substance is a powerful narcotic for her kind; it's both the main currency and the most common form of recreation in Hell - the actual torture is just a job for most demons.
In the first issue of Global Frequency the organization's MIT physics consultant provides a situational analysis while still wearing his gimp mask.
When 355 sends Yorick for therapy in Y: The Last Man it turns out that the process is an extended BDSM session with the therapist.
In Sin City, most of the female assassins of the Colonel's Guild are into S&M in one form or another. They are all very intelligent, battle savvy women. One of them is a genetics expert.
The Beef Boys from Wildcats 3.0 are never seen without their bondage gear, and the one who speaks (the other always has a ball gag when seen) is very intellectual.
Mildly inverted with Grimbor (the Chainsman), an adversary of the Legion of Super-Heroes; he is a brilliant man so long as it comes to restraints and bondage, but dumb in any other way; it reminds one of an idiot savant.
Edward from Secretary is an educated, successful lawyer who finds himself transitioning from the titular Secretary's boss to her dominant partner.
Severin in Shortbus, an educated, sympathetic woman who enjoys S&M.
Annie Savoy from Bull Durham reveals in one scene that in her day job she's an English prof at a community college. She's very given to quoting famous poets, and the first night she and Nuke Laloosh were together they didn't even have sex: she just tied him to the bed and read Walt Whitman to him all night. When she and Crash Davis finally get together it turns out she also likes being on the receiving end.
Judy Bernly, the brainy secretary of 9 to 5, is perceived to be into this by her ex-husband Dick when he catches her in the bedroom with her boss Frank Hart while she, Doralee, and Violet were holding him hostage.
Gravity's Rainbow includes a character expounding on the virtues of "sado-anarchism."
The End of Mr. Y has a measure of it. The heroine is every bit the brainy academic stereotype... and she likes to be bound during sex. Kinky.
Kushiel's Legacy is made of this trope. Terre D'Ange is by and large highly accepting of any sexual kinks, and while there's less talk among the general public about the S&M practices, they're also considered sacred. This view is magnified exponentially by the main character, who experiences pain as pleasure (the mark of her patron god). She is a high class prostitute, and engages in a wide range of masochistic sexual encounters. Many of these are portrayed as loving, cleansing, or just downright fun. The negative BDSM scenes are a result of true malice on the part of her client, and are portrayed as perversions of the kink, rather than the entirety of it. Moreover, Phedre is extremely intelligent, and the books often wax philosophical on the nature of pain, pleasure, and sexuality.
Tarl Cabot of Gor was a university professor on Earth and clearly an Author Avatar as the author John "Norman" Lange got his Ph. D. in philosophy from Princeton and teaches ethics at CUNY.
Vishous of the Black Dagger Brotherhood is a sexual dominant. It's not until the end of his book that he allows himself to be the one tied up and caned.
Accelerando states that BDSM is more popular than traditional sex in the near future timeline, as there's less chance of pregnancy or disease.
The KGB informant Professor Lyko in The Man from Barbarossa is into S/M, specifically to being pelted by oranges by his mistress.
Live Action TV
Dr. Chase from House is a brilliant surgeon who turns out to know the dominatrix whom one patient has been seeing - they used to hang out at the same BDSM club.
As well as another case where the boyfriend was suspected, until he was found tied and gagged. Quite the alibi.
In one episode of Castle the victim is a doctoral student who was a dominatrix. Her boss at the dungeon was a former lawyer.
Also, Beckett occasionally implies this, mostly to mess with Castle. And the first of the defictionalizedNikki Heat novels has a Sexy Discretion Shot away from one of these between the leads.
In the fifth season, at least one episode has implied that both Castle and Beckett have a taste for this in the bedroom.
Chuck and Blair are considered to be the most intelligent characters in Gossip Girl, and they have a lot of fun.
Dr. Charlotte Lewis, Sawyer and (hinted) Dr. Juliet Burke in LOST.
In the fifth season, Juliet is living in the village with her live-in boyfriend Lafleur who is actually Sawyer undercover. One evening they get a unwelcome visitor who has found evidence that there's something wrong with Lafleur/Sawyer. Lafleur beats him up and asks Juliet to get some ropes to pacify him. Without hesitation, she turns to the bedroom. Of course. Where else would she be keeping the ropes?
In episode eight of the sixth season, Sawyer is on a date with Dr. Charlotte Lewis. When she says she's an archaeologist he asks her if she's like Indiana Jones. When she says yes, he asks her if she have a whip. She smiles and says "maybe". One minute later into the episode they are naked in bed. Charlotte says "Wow. Not bad, considering we didn't have that whip", and Sawyer replies "Bring it next time". Both lines said while cuddling, and said in a very friendly tone of voice.
Worf and Dax in Star Trek: Deep Space Nine frequently end up in medical during the middle of the night with dislodged limbs and broken bones. While Worf is more of a highly traditional Proud Warrior Race Guy, Dax is a scientist with literally several lifetimes of experience first, and treats Klingon martial arts just as a sport. It's not explicitly said how they did it, but they certainly like it rough.
A lot of Klingons enjoy the rough stuff. On the same morning after Worf and Dax's first night together, Quark and Grillka also showed up in the infirmary with similar injuries. Data even once mentioned that in Klingon culture a broken clavicle during sex is considered a blessing on the future marriage.
But that's OK really because Klingons have a spare set of clavicles (don't ask how that works) along with redundant spares for almost everything, up to and including higher brain function - it's when they get involved with another species that problems occur.
In the Dollhouse episode "A Spy in the House of Love", Echo is first shown imprinted with a dominatrix personality, and waxes philosophical to Boyd that it's about trust rather than pain.
Implied in Doctor Who with the Doctor and Dr. River Song.
Probably skating the line here, but in Farscape you have Wicked CulturedMagnificent Bastard Scorpius who really has a thing for black leather and masochistic tendencies. Yes that way. However, this being Farscape, there are a lot of very intelligent people/aliens enjoying really kinky stuff. There is a reason it's been described as an American man's descent into the Australian BDSM scene.
Scorpius isn't a stretch at all. The first and only time Scorpius and Sikozu are...intimate...onscreen involves Sikozu sitting on Scorpy's lap while he wraps a rope around her neck. Yeah.
In the episode "Crackers Don't Matter," the mental clone of Scorpius implanted in Crichton's brain (It Makes Sense in Context), which had been previously encouraging him to slaughter his shipmates, advises him instead to tie Chiana up and "save her for dessert."
Hinted at in Angel with Wesley, who has Encyclopaedic Knowledge of demonology. In episode 2.20, we get the following exchange (while researching how to keep together while going through a dimensional portal):
Angel: "What, we handcuff ourselves together? Who do we know that has handcuffs?"
Wesley: "Well, I—" (pauses and looks uncomfortable) "—wouldn't know."
In Sherlock, a modern day version of the Sherlock Holmes canon, Irene Adler is a dominatrix who caters to the rich and powerful, using her "access" to gain sensitive material for blackmail and leverage. She's also, in every senseof the word, the only one to ever beat Sherlock Holmes, and much more thoroughly than in the original story. For a while, at least.
Sherlock: A power-play with the most powerful family in Britain. Now that is a dominatrix. Ooh, this is getting rather fun, isn't it?
Across the pond, Sherlock himself is an example in Elementary.
Joan Watson: There was a woman leaving just as I got here - did she get you high?
Sherlock: To about six feet. (takes his belt off a ladder with handcuffs dangling from it)
The full 18 minute version of Violet UK's Blind Dance, as it's an ethereal, lyrically beautiful exploration of sex and sexuality while being a Gothic Metal song about BDSM sex from the submissive's perspective.
Blue And Blind from Violet UK which is a reflective piece through the lens of craving submission in sex.
Vagrant Story: It's not quite clear why, but about half of the cast is walking around in BDSM gear. And spouting faux-Shakespearian dialogue.
Kinzie Kensington of the thirdSaints Row game, who was a FBI computer analyst and hints that she is a regular at a BDSM club that even squicks out the main character. Pierce even points out the leather dominatrix mask she keeps in her hacker cave, and pokes the Boss with a 3-foot dildo.
In The Witcher 2, when visiting Philippas home, one can find the archmage whipping her naked apprentice on her bed.
Though she hasn't had any sex, Gaige from Borderlands 2 is probably the kinkiest and flirtiest of the playble cast, complete with a pair of handcuffs. She's also the smartest, being able to build giant floating death robots and cyborg arms that can smash concrete with the tools in her backyard shed.
Equius in Homestuck is a play on this, as he has a submission fetish and a love of breathplay, as well as a ridiculously flowery vocabulary and an interest in building robots.
Ally, the main dominatrix in Sunstone, made her money being a software developer and computer programmer, and the rest of the cast aren't slouches either in the intelligence department. Given the general level of thought that's involved in creating and maintaining the illusion while at the same time keeping the person safe, it's clear that BDSM is a smart people's game.
This list is not restricted to bondage specifically, but it is notable.
Speaking of dommy ladies, The Nostalgia Chick's a parodied Brainy Brunette and has told anyone bitching about how Hercules being not like the Greek myths to "stick a ballgag in your mouth and sit in the corner".