Spy Couple

"98. If an attractive young couple enters my realm, I will carefully monitor their activities. If I find they are happy and affectionate, I will ignore them. However if circumstance have forced them together against their will and they spend all their time bickering and criticizing each other except during the intermittent occasions when they are saving each others' lives at which point there are hints of sexual tension, I will immediately order their execution."

- Evil Overlord List, promoting minimum of paranoia necessary for large scale nefarious activity

A Mix and Match of Spy Drama and Odd Couple. Often is lighter in tone than the usual Spy Drama.

Comic Books

 * Black Widow and Bucky Barnes.

Fanfic

 * Otacon and Adamska in the later parts of Stray.

Film

 * Mr. and Mrs. Smith: a married couple that are both assassins, unknown to each other until they try to kill each other.
 * Carmen and Juni Cortez in Spy Kids. Also their parents, grandparents and the Giggles siblings.
 * Jane and Jefferson Blue from Undercover Blues, complete with their toddler daughter.
 * Finn McMissile and Holley Shiftwell from Cars 2 are merely partners,

Literature

 * Mary Pat Foley and Ed Foley in The Cardinal Of The Kremlin.
 * Tommy and Tuppence Beresford, who appeared in four of Agatha Christie's novels and one short story collection.
 * Boris and Irina from Tinker, Tailor, Soldier, Spy, though theirs is described as a common-law marriage and the former may or may not be aware of the latter's status.
 * Cammie & Zach from Gallagher Girls
 * Hellstrom's Hive starts with Depeaux and Tymiena trying to spy on a suspicious farm.

Live-Action TV

 * Michael and Nikita from Nikita.
 * Chuck Bartowski and Sarah Walker from the television show Chuck.
 * I Spy
 * The Man from U.N.C.L.E.
 * The Avengers
 * Get Smart is a parody of this genre (among other things).
 * Scarecrow and Mrs. King featured a particularly Odd Couple, in which one was an experienced agent (Scarecrow, played by Bruce Boxleitner) and the other was Amanda King (played by Kate Jackson), a normal housewife complete with divorce, two kids, and live-in mother, who got involved in Scarecrow's spy hijinks in an amusingly contrived setup.
 * Adam and Fiona from Spooks actually were a Spy Couple, albeit in a darker toned drama. Until Fiona got killed by an annoyed Syrian. Adam
 * Michael and Fiona in Burn Notice move in, out, and between this trope like it's nobody's business.
 * Alias has alpha couple Sydney Bristow and Michael Vaughn, who are a heroic version. Beta Couple Jack Bristow and Irina Derevko (Sydney's parents) are a different version - playing it straight at points in Season 2, and subverting it whenever Irina decided she was working for other people.
 * The entire premise of Undercovers.
 * Joan and Arthur Campbell in Covert Affairs, who are the Beta Couple to Will They or Won't They? couple Annie and Auggie.
 * So far Annie and Auggie are Like Brother and Sister with Auggie acting as the big brother.

Video Games

 * Snake and Otacon from Metal Gear Solid.
 * Sasha Nein and Milla Vodello from Psychonauts. Is there any question why?

Web Comics

 * The Continentals: A steampunk murder, mystery, adventure webcomic set in post Jack the Ripper England where Continental Operative Jeffrey Tiffen Smythe and his gender bending partner the adventuress Lady Fiona Fiziwigg investigating a series of brutal "mangling" murders uncovers a tangled web of intrigue, adventure—And murder!!! Find it here.

Western Animation

 * from Recess
 * Kim Possible and Ron Stoppable in Kim Possible.
 * Fillmore! and Third, although they aren't particularly odd.

Real Life

 * It has been known for the wives of CIA agents to assist their husbands on ops. In the dehumanizing eyes of authority, the wife is effectively an agent and the husband is The Handler. With due allowances made for the mundane Real Life of espionage it can actually resemble this trope, not least if the couple are close. However there is a dark side in that the unofficial status of CIA wives can give The Government an excuse for ingratitude.
 * This of course refers to situations when only one is officially employed. The record doesn't seem to show many cases where both are officially employed and used in a team though that does not mean it never happens (this is, after all, espionage we're talking about).
 * See Spies Wives for more information:
 * Additionally, the agent may be married to someone else who has government business, and they may support each other (if sometimes unwittingly) that way. Valerie Plame, for instance, is married to Joe Wilson, a career Foreign Service Officer.
 * A spouse or family member of a career diplomat engaging in espionage actually isn't rare... as these people have diplomatic immunity. It would be more of a surprise if a major embassy were not spying on the host nation.
 * Of the ten Russian spies arrested in the USA in 2010, eight were married spy couples.
 * Hu Simeng and Horst Gasde were a married couple in Berlin who acted as triple agents and played every agency in the area for fools.
 * The authors of The Company We Keep: A Husband-and-Wife True-Life Spy Story.