The upcoming handheld system was shown running the communication tool at a demonstration in Brazil, Gaming Generation reports.
Vita's predecessor, the PSP, also supports the service, but there was some doubt over whether it would be compatible with the new platform due to competitor Microsoft's recent acquisition of Skype.
Microsoft will honour its pledge to uphold existing Skype service contracts and continue to offer the tool to non-Microsoft users.
Skype has more than 170 million users worldwide. It is estimated that 600,000 new users sign up for the service each day.
PlayStation Vita will be released at the end of the year.
> PlayStation Vita priced at £230 by UK retailers
Watch the PlayStation Vita E3 reveal trailer below: