My friend Juice asked me to look into this website for her. She remarked that it could be "interesting, but scary". After checking it out, I figured out why. I also figured out why, being married, she could not check it out herself first.
The premise is interesting - video chat with random people around the world (the whole thing is supposed to be randomized). If you see someone you don't like, click NEXT. If you see something you like, stick around and chat it up. The reason I say "something" is because you don't always see people, but rather parts of people or couples in uncompromising positions, and that can be unsettling and vile after a while. According to MyAnh, who reviewed Chatroulette earlier today, the site seems to have cleaned itself up, but when I tried it a few months ago, that wasn't the case. When I explored it, it was a mature site, not to be visited by children, yet there were children on it, and I felt the sudden need to protect them.
I don't think the site is necessarily bad, but it can be disillusioning to see how uninhibited and lonely some people seem to be. And even when someone appears to be a respectable person to get to know, he may reveal his real motives with time, so take heed and be careful there. I'm also not a fan of NEXTing someone, in the spirit of MTV; I can't imagine how hard it must be for some folks to be nexted over and over again.
In short, while the idea is promising - to connect people from around the world, I feel like this is more of a social experiment that could potentially be damaging, if not better thought out.