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[oneup]

Worms Armageddon is awesome. I'm sure a lot of other turn based games a great for hanging out in. Although it tends to take forever to get through a game in those. Wesnoth might be alright for some quicker matches. Oh, and we played through most of Neverwinter Nights 2 together. It was alright.

isn't there a worms out for Xbox Live Arcade?

[Cymon]

Diablo 2 and GTA 4 are really good co-op games.

Oh,

And Castle crashers will own all co-op games ever. Seriously.

So why don't they port it for PC already!

[MekanikDestructiwKommando]

I haven't gotten a rom to work yet, but I've talked to people who say it plays great:
http://ggpo.net/ -- "Newfangled lag algorithm to minimize lag in fighting games"

[Dragonmaw]

The best suggestions in this thread so far are Worms, Civ 4, and TF2.  They are all great games to chat to.  TF2 is a game of constant action, yeah, but once you know your role, you really don't think about it much, letting you do real conversations.

From personal experience.