The Australian Less Wrong meetup runs Google hangouts. I find these valuable because I don't have the time to attend Less Wrong hangouts in person. I would recommend that other groups consider running these too.
There is also a Less Wrong group on IRC.
Awesome Google Hangouts is also a fantastic idea. I gave the IRC chat a look, and the Skype group idea is still open as that is more of a smart-silly-chatroom according to the people there, but it is a really good first order approximation. Thanks!
Are there any LessWrong Skype groups, or active live chatrooms? I've been looking around and found nothing. Well, with the exception of the LW Study Hall, but it doesn't quite fit since it is primarily for social work/study facilitation purposes with only minor breaks. This would fulfill a primarily social function.
But you ask, wouldn't a regular Skype chat reduce effectiveness by distracting people from their work? A little bit, but I'd rather the distracting thing be increasing my rationality by getting me engaging in the ideas with other people who are actively trying to do the same. I expect it to have an overall positive effect on productivity since I am bound to encounter one or two ideas to do so.
Thus, the value of such a group for me would be to discuss topics pertinent to rationality, and increase increase the shininess and entertainment value of LessWrong's ideas- it is already pretty interesting, and I've had fun thinking while sitting around reading the Sequences (finished How To Actually Change Your Mind not too long ago). There are no meetups near me, and I'd rather engage via online interactions anyway.
If there is no such group already, I'd be happy to start one. Feel free to either leave your Skype name in the comments or send me a PM if you're interested.
edit: My Skype id is bluevertro