Unfortunately Skype is not currently available on the BlackBerry PlayBook, though it is officially available for devices such as the BlackBerry Q10 & Dev Alpha C, soon for the Z10 when it updates to 10.1. I think there is a possibility that the PlayBook will get Skype after BlackBerry 10 is made available for the PlayBook itself. For the meantime I suggest using FaceFlow Video Chat via the PlayBook Browser. Or, if you prefer; Check out http://imo.im and use Skype through the browser.
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