Froome goes into the race as one of the leading contenders having crashed out of defending his Tour de France title in July.
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“I’m really pleased with how my recovery has gone since the Tour, I’ve been training hard and the support team are pleased with my progress,” said Froome. “I’m a little bit light on racing days this year so getting a Grand Tour under my belt will not only help me now, but it will also help my preparation for next year.
“Going for the win will certainly be tough, but we’ll give it everything we’ve got.”
Froome will be joined by fellow British riders Luke Rowe and British road race champion Peter Kennaugh, the latter of which has enjoyed success after being overlooked for the Tour de France with overall victory in the Tour of Austria.
Bradley Wiggins was not named in the line-up, and he is expected to defend his title in the Tour of Britain (September 7-14).
Along with Froome, Kennaugh and Rowe, Sky will start Philip Deignan, Mikel Nieve, Vasil Kiryienka, Kanstantsin Siutsou, Christian Knees and Dario Cataldo in the race.
Team Sky principal Dave Brailsford said: “This year’s Vuelta is a great opportunity for us to get back to Grand Tour racing and I’m delighted that we’ll go there with a strong team that’s very capable of performing well.
“Chris Froome will be our team leader and it’s great to have him back on the bike and focused on the challenge ahead. He was obviously very disappointed after having to withdraw from the Tour de France but Chris has recovered and trained well since the injury. He’s now more determined than ever to get back to what he does best – riding Grand Tours.
Orica-GreenEdge selects British neo-pro Adam Yates for his Grand Tour debut at the end of August
Provisional list of starters for the 2014 Vuelta a Espana, August 23-September 14