Littleford left UKTV last month after four years spent overseeing the BBC Worldwide-Virgin Media joint venture's portfolio of channels, including Dave, Really and Good Food.
According to C21 Media, Littleford will now oversee the editorial proposition for global iPlayer, which is due to launch in the US on Apple's iPad this summer. He will report to Jana Bennett, Worldwide's president of global networks and international iPlayer.
"Matthew's knowledge of great British content is second to none. For the past four years he has worked with UK broadcasters and the independent production community to fill the schedules of the 10 excellent UKTV channels," said Bennett.
"We're very pleased to have him onboard as we move to take the best British programmes to new digital audiences overseas."
Littleford added: "The British television industry can be extremely proud of its quality and variety - something that is already recognised the world over. Having the opportunity to deliver this content via the latest digital platform is an opportunity I couldn't resist."
Last month, BBC director general Mark Thompson revealed that the international version of iPlayer will cost subscribers less than $10 (£6.13) a month when it launches later in the year.