Agassi and Graf - who are husband and wife - will join Kim Clijsters and Tim Henman for a series of exhibition matches on May 17, five weeks before the Wimbledon tournament.
The event - dubbed "A Centre Court Celebration'' - is designed to test the new roof and air management system with live matches in front of a capacity crowd of 15,000.
The program will feature a men's singles, a women's singles and a mixed doubles match. The matches will be played in a pro-set format - the first to eight games, with a tiebreaker at 8-8.
Tickets, which will cost 35 pounds ($50), will go on sale March 12.
The new sliding roof will help alleviate Wimbledon's perennial rain delays.
The traditional roof overhang on Centre Court was removed after the 2006 tournament, leaving the grass surface more open to the elements in 2007. The overhang was back in 2008, along with 1,200 extra seats.
This year's Wimbledon tournament will be held June 22-July 5.
"Though this project has been a sophisticated engineering feat, we always wanted to capture the essence of Wimbledon's history and tradition in a new, modern Centre Court which itself would still be celebrated as the stage of some of the most memorable moments in tennis,'' All England Club chief executive Ian Ritchie said.
"With players of the caliber of Agassi, Graf, Clijsters and Henman this test event promises to be hugely entertaining. Brilliant players, great tennis, an iconic venue and the chance to be part of Wimbledon history - what more could one want?''
Agassi, who retired in 2006 with eight career Grand Slam titles, won Wimbledon in 1992 and lost in the 1999 final to Pete Sampras.
"I have great memories of playing at Wimbledon and to be among the first to play under the new Centre Court roof is really exciting,'' he said.
Graf retired in 1999 with 22 major titles, including seven Wimbledon crowns.
"There is no tennis venue more special to me than Centre Court at Wimbledon,'' the German said. "It just doesn't get any better. I couldn't be more honored to play there again with my husband Andre, and tennis greats Kim and Tim. It will mean so much to return to Wimbledon and ... relive so many wonderful memories.''
Clijsters, the 2005 U.S. Open champion, twice reached the Wimbledon semifinals and retired from tennis in 2007. Her only career match against Graf came in a fourth-round loss at Wimbledon in 1999.
"It was quite an experience,'' Clijsters said. "I was very nervous to play against my idol and because of the rain the match took two days to finish. The new roof will prevent that this time around.''
Henman, Britain's former No. 1 player, reached the Wimbledon semifinals four times.
"Wimbledon's Centre Court was always a special place for me,'' he said.
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Agassi, Graf to play first matches under new roof