•Bucky Barnes, Captain America's sidekick, was created by Joe Simon and Jack Kirby in 1941's Captain America Comics #1. His Winter Soldier look, identity and backstory as a brainwashed assassin with a robot arm were the creations of Ed Brubaker and Steve Epting. Barnes first appeared as the Winter Soldier in 2005's Captain America #6.
•La Contessa Valentina Allegra de Fontaine, an agent of the espionage team SHIELD, was created by Jim Steranko in 1967's Strange Tales #159.
•Red Guardian Alexei Shostakov, the Soviet Union's answer to Captain America, was created by Roy Thomas and John Buscema in 1967's Avengers #43.
•Taskmaster, a mercenary and combat instructor with "photographic reflexes" that allow him to mimic the moves of his opponents, was created by David Michelinie and George Perez in 1980's Avengers #196.
•John Walker, a one-time Captain America antagonist, was created by Mark Gruenwald and Paul Neary, appearing for the first time in 1986's Captain America #323, wherein he used the name "Super Patriot." He later became the new (and temporary) Captain America, before finally settling on the name USAgent in 1989's Captain America #354. I'm afraid I'm not sure which artist deserves credit for the black, white and red variation of the original Simon and Kirby Captain America costume that Walker eventually adopted as his USAgent get-up. (Tom Morgan seems to have penciled its first appearances). If you know, please tell us in the comments and I'll update this post.
•The Ghost, an Iron Man villain with a power suit that allows him and objects in his possession to become invisible or intangible, was created by David Michelinie and Bob Layton in 1987's Iron Man #219.
•The Thunderbolts, a group of long-time Marvel supervillains who secretly adopt new codenames and costumes to pose as a superhero team, were created by Kurt Busiek and Mark Bagley for the 1997 Thunderbolts series (Although they first appeared in The Incredible Hulk #449 by Peter David and Mike Deodato Jr.).
•Yelena Belova, the second Black Widow, has some rather convoluted creation credits. She first appeared as a sketch by artist J.G. Jones in 1998's Marvel Knights Wave 2: Sketchbook #1, made her first in-story appearance in a 1999 issue of Paul Jenkins and Jae Lee's miniseries Inhumans and then starred in a 1999 Black Widow miniseries by Devin K. Grayson and Jones, who are usually credited as her creators. (Wikipedia lists Grayson, Jones, Jenkins and Lee all as her creators, though). She is, obviously, a legacy version of Black Widow Natasha Romanoff, who was created by Stan Lee, Don Rico and Don Heck for the Iron Man feature in 1964's Tales of Suspense #52. She has since adopted the name White Widow.
•The Sentry, a Superman analogue with mental health problems that manifest as the alternate identity The Void, was created by Paul Jenkins, Jae Lee and Rick Veitch for 2000's The Sentry #1.
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Speaking of who created The Sentry... You'll note that I credited Paul Jenkins, Jae Lee and Rick Veitch above. As you've probably noticed, I was going by Wikipedia's credits for all of those I didn't already know. A few months ago, I would have told you that Jenkins and Lee created The Sentry, but then, that was before I stumbled upon this interview with Veitch at the website Popverse, which includes various sketches of the character in the style of different artists apparently created to support a pitch. It's a fascinating (if rather sad) interview, and paired with this follow-up story, it seems like Veitch and Jenkins are currently in rather strong disagreement about whether or not Veitch contributed to the character's development at all.
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