Connecting PS3 to PC for audio?

Well, the first one is designed to split a 3.5mm signal into 2. For example, you could use it to connect a single iPod to 2 different sets of headphones.

I believe the second one is what you are looking for. It allows you to connect RCA jacks to a 3.5mm socket.

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If the cables look like that, then yes. Number 2 is what you are looking for.
 
That applies to all 3.5mm jacks. They can only transmit stereo. Your going to have to use optical or the colorful 3.5 mm ports if you want 5.1.