Stubbs will start his new role on August 15 when Everton play Arsenal in the first game of ESPN's 46 matches for the 2009/10 season.
He will also oversee Liverpool versus Aston Villa on August 24, Tottenham Hotspur versus Manchester United on September 12 and Chelsea versus Blackburn Rovers on October 24.
Speaking about the new role, Stubbs said: "Having been associated with the BBC for over 25 years this was always going to be a difficult decision. But the opportunity of joining one of the world's leading sports broadcasters on day one of the new ESPN channel in the UK was just too good to turn down.
"I can't wait for the start of the new season and the trip to Merseyside for ESPN's first game at Goodison Park. I would like to thank all my BBC colleagues for their support and friendship over the years."
ESPN EMEA managing director Lynne Frank said that she is "absolutely delighted" that Stubbs has agreed to join the channel's English Premier League commentary team.
She explained: "Ray has a vast amount of experience hosting the biggest sporting events in the UK and, as a very familiar face to football and sports fans across the UK, signals our intent to secure top talent to present our growing sports portfolio in this country."
In reaction to the move, BBC head of TV sport Phil Bernie added: "Ray has been a fantastic member of the BBC Sport team for many years and we wish him all the best for the future."
The ESPN channel has already been announced for carriage in standard and high definition on Sky's EPG, while negotiations are also underway to bring it to BT Vision and Virgin Media.