The 50-year-old, who won twice on the main European circuit and was a past chairman of the tour's tournament committee, was appointed to the voluntary post by the British Golf Association in preparation for golf's return to the Games for the first time since 1904.
"I'm honoured to have been chosen for this role," said Spence, who is currently the European Tour's director of player relations and is also involved in coaching and television analysis. "Going to the interview was like the feeling I had being on the first tee of the Open; I still have that same excitement."
The selection criteria for the golf event has still to be finalised by the International Olympic Committee but is expected to be based on the world rankings, with a maximum of four male and female players per country.
Northern Ireland's Rory McIlroy and Graeme McDowell have yet to decide whether to represent Great Britain or the all-Ireland set up that remains in team golf.
Before all that, however, there is business to be done in Abu Dhabi this week. Phil Mickelson, the Open champion, will makes a rare European Tour when he competes in the $2.7m HSBC Abu Dhabi Championship.
The first event of the tour's annual Middle East swing, which also includes the Qatar Masters and Dubai Desert Classic, starts on Thursday and features Mickelson and three other top 10 players: Henrik Stenson, McIlroy and Sergio Garcia.
Mickelson, the American left-hander ranked fifth in the world, will be making his second appearance in Abu Dhabi having tied for 37th place in 2011.
Twelve months ago Welshman Jamie Donaldson claimed the biggest tournament victory of his career, eclipsing a strong field including McIlroy and 14-times major winner Tiger Woods to lift the Falcon Trophy. "It was a great win," said Donaldson. "Going back anywhere that you've played and won before is really good."