The big blinking one you’re missing is Matt Murdock. He’s probably the superhero Natasha has the strongest ties to, though that’s been obscured a bit lately with all the Secret New Avengers Assemble branding they’ve pushed and the no ninjas allowed Daredevil relaunch.
Fandom makes her close with Steve, sometimes, but I’ve generally seen her as having stronger ties to Tony. As for the other Avengers, that book hasn’t really done a great job building Natasha’s relationship with anyone not named Clint Barton. (Historically, I’d say it hasn’t done to great building Natasha on the whole, though I think the movie and certain Warren Ellis comics made it obvious there’s a lot of potential there.) I think Spencer and Remender both talked about developing a friendship between Natasha and Brunnhilde, so idk maybe that happened off panel.
There are assorted supporting characters introduced in Natasha’s own books: Black Rose, Phil Dexter, Sally Anne Carter, going back to Irma Klauscichnova, Annie Baxter, and Paul Hamilton, and more names that no one’s gonna recognize, forming a respectable corps of sketchy spy friends and dudes or damsels in distress. These characters tend to last one writer, and since the longest anyone’s written Natasha is for twelve issues…
Yelena Belova and Ivan Petrovich have lasted a bit longer as supporting characters but are very inconsistant about being Natasha’s friend.
There are also characters Natasha’s developed friendships with in other corners of the MU. She has a real habit of reaching out to younger female heroes, i.e. Rikki Barnes and Laura Kinney, going back to Darkstar, kinda. Her friendship with Dagger (of Cloak & fame) is probably the most developed of these, and they even lived together for a while!! There’s also Angela del Toro and Helen Kim, who definitely developed into friend territory for me. There was even that team-up story with Rogue a while back that I had some problems with, but I really love the idea of that friendship regardless.
Anyway, while Natasha’s not the most approachable person in the world, and she tends to be all-business in her superhero mode— I really don’t think she’s unfriendly. She has too many random spy contacts who would die for her, even from the old days, too many personal loyalties. But it’s, uh, easy to get lost in continuity.
Rebloggable by request.