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PSN
has all functions that LIVE has accept cross game voice chat. so if you are both playing the same game then you can voice chat if playing to different you have to use Text Chat, but they are brining voice chat out very soon.
along with everything live has you also get chat rooms so you can talk to loads of diffrent people at the same time

PSN also has the best services:

Playstation Home - Dont let people tell you its rubbish and its failed, it really hasnt! around 8 million people use it which is about the same amount of Live players who can actually play online to put it into comparision. Its great to see new games and meet up with friend before game launching, its also good to just kill half hour

Vidzone - Watch thousends of music videos online for free, i love this service and this alone puts PSN above anyother online Service

Video Store - you can Download thousneds of movies insted of buying them on DVD/Blu its great, plus if you want a night in you can rent loads of flims aswel so no need to go out to blockbuster, the Movie store has more films on it then any other platform

Playstation Store - AMAZING! the games you can download are sooo good like Flower and the Pixal JunK series, its got the most inative and amazing games on it

Netflex - i wont go into it unless you live in the US?

the PS3 really does do everything and is such a good value for money. The online is unmatched when it comes to the scale of things you can do. Plus....Wifi is built in AND its free to play online! on the 360 (not bashing it just pointing out) its an Extra £100 on top to get wi-fi and get online

PSN also has around 20million people that can actually play online, there are alot more people on the service to play with

 

sorry about all the spelling mistakes, im typing fast lol