This’ll end my weekend, back to commissions.
If anything, it could work because unlike so many of Peter's girlfriends, Carol is essentially the Marvel equivalent of Super-Girl. I don't think he'd need to worry about putting her at risk with the powers she has. Hell, HE'S probably more at risk from HER foes than she is of his!
Kaine (scarlet spider) and (any woman. you choose xD)
Miles Morales and Spider Woman
Seriously, if Superman and Wonder Woman can be a couple in canon why not these two?!
(Granted I liked Spider-Man's past marriage with MJ, but still come on, how many other heroines can you think go well with Pete?)
That said, if they ever did, I'd love to see Carol/Peter.