Zingarelli, who was Vodafone's global director of networks and service platforms, takes over from Babelgum co-founder Erik Lumer, who will instead focus on strategic product development.
Silvio Scaglia, Babelgum chairman and co-founder, said: "We are now moving to phase two in the development of Babelgum. The core technology has been proven and while our focus right now is on bringing together compelling content, we will soon turn to user acquisition and advertising. Valerio's appointment is a reflection of that changing focus."
Other priorities include launching a marketing campaign, aimed initially at English-speaking viewers globally and looking at building advertising revenue.
Zingarelli said: "Babelgum is right at the heart of a revolution in television, building a truly personal global media capable of delivering a huge amount of professional television quality content to millions of users around the world."
Prior to joining Vodafone, Zingarelli was an independent member of the board of fixed line telecoms company Fastweb.