The 25-year-old has decided on a switch to the Aviva Premiership after spending seven years with Cardiff Blues.
James has made 10 appearances for Wales as well as over 100 league and cup appearances for the Blues, for whom he has scored 39 tries.
He told Exeter's official website: "Signing for Exeter Chiefs is a great move for me. They are a team that I've watched come up to the Premiership over the last few years and do really well.
"I've had a fantastic seven years with the Blues and I am very grateful to have been given the opportunity to play for them and for the support I've been shown over my career. But I felt the time was right for a fresh challenge.
"Exeter are clearly an ambitious club and having talked to the coaches about where they want to go and also the plans for the stadium, I felt I wanted to be a part of it all and experience something different."
Gilbert has released a new line of rugby cleats. The Gilbert Virtuo 8S is part of the exciting new product. Check it out.
The entire All Blacks apparel line has been updated for 2013/14. Check out the New Zealand All Blacks polo.
The Nike Tiempo is a solid rugby cleat and one of few styles still made from full-grain natural leather.
The Gilbert Blitz 8S rugby cleat is a great cleat at a great price of $69.99. Get a new pair of cleats today.
A cool looking all black rugby cleat with the high performance adidas is known for. Get in the Gear!
Wear the crest of the British and Irish Lions on your t-shirt. A great look for the summer.
$29.99
The All Blacks Performance t-shirt is black with hints of blue from the training jersey. Very Cool.
The New Zealand All Blacks training jersey for 2013/14. Get in the Gear!
The USA Rugby Pro Alternate rugby jersey is perfect for any fan of the Eagles. Get yours to wear during the summer Test matches.
The NEW All Blacks 2013/14 jersey has arrived at World Rugby Shop. Dare to wear the colors of the All Blacks.
