The BBC Formula 1 host will start work with BT in January 2013 when its four-year football deal starts.
Humphrey's credits at the BBC include hosting children's series Sports Round, fronting coverage of Euro 2012 in Poland and Ukraine, covering the London 2012 Olympics and co-hosting the BBC Sports Personality of the Year.
BT has won the rights to air 38 live games across three seasons, including 18 'first pick' matches.
The presenter will host live coverage of the 38 matches and will also be involved with BT's creative teams and production partners, who are developing other football programming.
Humphrey said: "I am incredibly excited to be joining the team at BT not just because I get to fulfil a lifelong dream of presenting the Barclays Premier League but because of the fresh perspective that BT will bring to both sport and broadcasting in this country. To be a part of this young, vibrant team who are as passionate about sport, as I am, is a privilege.
"I've grown up at the BBC, and whilst I hope to work with them in the future, I'd also like to place on record my thanks to them. I am incredibly grateful to all colleagues, and of course the viewers, for their incredible support from CBBC all the way to Formula 1. My focus from the start of 2013 is on making BT's coverage of football the best this country has ever seen."
Marc Watson, chief executive of BT Vision, said: "We are absolutely delighted that Jake has chosen to join our new sports channel to anchor our Premier League programming.
"Jake is a tremendously experienced and popular sports broadcaster and a fresh, young and innovative talent. He impressed us with his willingness to get deeply involved in the development of our live football programming and we took into account his track record of excellent presenting across many sports. He fits our plans for the new channel perfectly and we are very excited to be working with him."