Shaw, whose most recent role was as global innovation director for O2's parent company, Telefonica, has been briefed to make the Skype system more widely available on mobiles.
As marketing director at O2, he was responsible for negotiating the sponsorship deal that created The O2 music venue on the site of the former Millennium Dome in London.
'Skype is an incredible brand that has grown spectacularly as a result of positive word-of-mouth and great end-user experience,' said Shaw.
Skype is reviewing its advertising arrangements in the UK. The account is held by Albion.
Shaw will take up his role at Skype on 1 September.
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