Englishmen Ian Poulter, Justin Rose, Luke Donald and Lee Westwood set off first at Medinah Country Club, with Northern Irish duo Graeme McDowell and Rory McIlroy in the second group along with Scot Paul Lawrie and Spaniard Sergio Garcia.
Germany's former world number one Martin Kaymer, Belgian Ryder Cup rookie Nicolas Colsaerts, Italian Francesco Molinari and Swede Peter Hanson then lined up in the third group on the first day of official practice for the 39th Ryder Cup.
"We have quite a lot of players that have done well in the past, and then I've tried to mix ... guys that I believe can complement each other and who understand each other really well," Olazabal told reporters.
"That's why I put Paul Lawrie with the Northern Irish guys and Sergio, because Sergio is a guy that gets close to everyone; he can play with anyone.
"The last four guys, that's where we do have four different nationalities, young guys, and we are trying to just figure out certain things still."
Good friends Poulter and Rose, who dovetailed superbly at Valhalla four years ago where they won two-and-a-half points from a possible three, are expected to be paired together for Friday's opening foursomes matches.
The 'Super-Mac' combination of McDowell and world number one McIlroy clinched one-and-a-half points from a possible two at Celtic Manor, Wales in 2010.
Olazabal has two previously successful routes to follow when it comes to matching up the rock-steady Donald.
In tandem with Garcia, Donald has won four-and-a-half points from a possible five in foursomes matches dating back to the 2004 Ryder Cup.
However, the Spaniard did not play at Celtic Manor two years ago due to poor form and Donald partnered Westwood to hammer the heavyweight American duo Steve Stricker and Tiger Woods 6&5 in the foursomes.
As far as 2010 US Open champion McDowell is concerned, Europe's eight players for Friday morning's foursomes are virtually set in stone.
"The established partnerships are fairly obvious: myself and Rory, Poulter and Rose, Donald and Garcia, perhaps Westwood and Lawrie," McDowell said before setting off for practice.
"There's your eight, the first two groups today, fairly predictable. You can pretty much predict our first eight players Friday morning. Will we be that predictable? Who knows.
"But I'm looking forward to seeing how the next three days pan out in practice and how Jose kind of assembles us all," added McDowell who secured the winning point for Europe in 2010.
The 7,658-yard No. 3 Course at Medinah has been set up with virtually no rough for this week's competition as US captain Davis Love III hopes to give his array of big hitters something of an advantage.
Olazabal, however, liked the look of the par-72 layout.
"The golf course is the same for everyone," the Spaniard said. "We have strong players on both sides ... and they can adjust to any situation.
"I think you're going to see a bunch of birdies this week. It's going to be a great show in that regard for the crowds. You're going to see holes tied with birdies.
"You'll have a few holes where anything can happen - like 15, 16, 17 - risk and reward holes. It's exciting. The way the golf course is set up is great."
Europe have triumphed eight times in the last 13 Ryder Cups and regained the trophy with a nail-biting victory by 14-1/2 points to 13-1/2 two years ago.