The former chief business officer responsible for strategy at The Times and The Sun, replaces Iain Holden who is leaving Sky having led the Business division since its inception in 1999.
Mike Darcey, chief operating officer of Sky, thanked Holden for his "significant contribution" during the past 19 years.
He said: "Under Iain's leadership the team has taken Sky into tens of thousands of commercial premises where audiences of more than five million now enjoy live sport each week."
Rey will begin his new role on 5 March and will report to Darcey. His new remit will be to grow the penetration of Sky Business' products and services – including WiFi, 3D and HD – as well as to evolve Sky’s pricing to ensure that even more pubs and clubs are able to realise the commercial benefits offered through live sport.
He joins following the recent conclusion of the European and UK court rulings on the use of foreign satellite services, which effectively prevents pubs from airing Sky’s branding and music around live football without paying for the service.
Sky and ESPN are the only broadcasters authorised to show Premier League football in pubs and clubs, and part of Rey's new duties will include managing heavy marketing activity promoting Sky’s sports package.
Darcey said: "Following the recent clarification on the use of foreign satellite services, Sky Business is now entering a new phase and I’m delighted that David will be on board to build even closer relationships with our commercial customers."
Rey's arrival will mark a return to the satellite broadcaster, having previously held the role of commercial director at Sky during a 12-year stint between 1996 and July 2009.
He left the broadcaster to become chief operating officer of Discovery Networks Europe before assuming his current role with News International.
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