Skype for Vita has been updated to 1.6, which allows for voice chat during gameplay with anyone on your Skype contact list (and seamlessly in the background as you transition between any apps, games, etc).
Also, if you receive a call while in a game/app, it will ring with the familiar Skype ringtone, and upon pressing the PS button, you will immediately be able to answer the call.
Pretty awesome stuff.
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