ESPN's first live English Premier League game of the season will be Everton v Arsenal at Goodison Park.
ESPN secured collapsed broadcaster Setanta's rights to 46 EPL games in the 2009/10 season in June.
Ray Stubbs said it had been "a difficult decision" to leave the BBC, but the opportunity of joining one of the "world's leading sports broadcasters" on day one of the new channel was just "too good to turn down".
Lynne Frank, managing director, ESPN in Europe, Middle East and Africa, said Stubbs has a "vast amount of experience hosting the biggest sporting events" in the UK and, as a familiar face to sports fans, his appointment signals ESPN's intent to secure top talent to present ESPN's "growing sports portfolio" in the UK.
An ESPN spokesman said it plans to make its Barclays Premier League coverage widely available across multiple pay-TV platforms. Initially, the coverage will be retailed by Sky to residential and commercial customers.
Yesterday (16 July), BSkyB and ESPN struck a £65m deal with the Scottish Premier League to air 60 live Scottish Premier League matches each season across the UK and Ireland.
Aegis Media's Carat has been appointed to handle ESPN's media planning and buying in the UK.
ESPN is understood to have paid about £250m to air 46 games for the 2009/2010 season and 23 games in each of the three following seasons.
Sky Media will be sales house for ESPN's new EPL-focused channel and the multimillion-pound deal means Sky Media will handle ad sales around every EPL match aired live on UK television.
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