Yes and no. I've been collecting all along, but very (too?) selectively.
I snagged a couple of early Spidey's but not necessarily the one's I want. I skipped Rhino repeatedly unfortunately, as it is the best done of all the villains to this point, IMO. I grabbed Hobgoblin and am very pleased with it. The rest of the villains I've looked at a decided on a case by case basis.
Morbius - disinterested. Wanted it, saw it, passed.
Kraven - repeatedly crappy paint jobs, did not pick it up.
Green Goblin - got it, but had I seen pics of the S6 box set, I would have passed. It's kind of cool, but more modern than I would like.
Daredevil - no, not a villain, but crappy paint prevented me from picking this up as well.
None of the other spidey figs did anything for me, in spite of comments here. I don't need too many spidey's, especially if they don't differ substantially from each other. I do have the daredevil from series one (both red and yellow) and I'm trying to acquire the black spiderman. I might snag other spidey figs at some point, but only at below retail pricing, if that can happen.