Novak Djokovic will begin his Wimbledon title defence in the opening match on Centre Court at 13:00 BST on Monday.
The Serbian faces Juan Carlos Ferrero and is followed on court by women's world number one Maria Sharapova, who takes on Anastasia Rodionova.
Third seed Roger Federer meets Albert Ramos second on Court One, with Kim Clijsters third in the same arena.
Britons Joshua Goodall, Oliver Golding, Heather Watson, Naomi Broady and Johanna Konta also feature on day one.
On all courts other than Centre and One, play will start at an earlier time of 11:30 this year.
Goodall will be the first home representative in action when he meets fellow wildcard Grega Zemlja of Slovenia second on Court Three.
Broady faces Lourdes Dominguez Lino third on Court 16, with Golding taking on Russia's Igor Andreev fourth on Court Two and Konta playing Christina McHale of the United States last on Court 17.
Watson's encounter with Iveta Benesova of the Czech Republic is yet to be given a court and neither has the doubles first round involving Jamie Murray and American partner Eric Butorac against Andre Begemann and Igor Zelenay.
Dominic Inglot and Philippine team-mate Treat Conrad Huey are fourth on Court Nine against 19th seeds Jonathan Elrich and Andy Ram.
But the main attraction is Djokovic - back at Wimbledon for the first time since and starting of his bid for a sixth Grand Slam title.
He has a 1-1 head-to-head record against Spaniard Ferrero but those meetings came in 2005 and 2007.
Ferrero, a two-time Wimbledon quarter-finalist, topped the rankings in 2003 - the year he won the French Open and reached the US Open final - but the 32-year-old is currently 38th in the world.
"He was the idol of many generations back in Spain," said Djokovic. "He's a Grand Slam winner, a Davis Cup winner and somebody that people really appreciate.
"Everybody who follows tennis, especially us players, respect him a lot. He is always dangerous. I think he's playing as well as he was four or five years ago.
"He definitely has a lot of experience on the big stage, so I'm not underestimating him."
Fresh from her maiden top seed Sharapova is hoping to win Wimbledon for the first time since lifting the trophy as a 17-year-old in 2004.
She faces 133-ranked Rodionova having won all four of their previous encounters, but the most eye-catching women's match on Monday sees Clijsters face 18th seed Jelena Jankovic.
The 29-year-old retires at the end of the season and will hope to mark her final appearance at the All England Club with a first title.
Rafael Nadal, Andy Murray, Petra Kvitova and Anne Keothavong are among the players starting on Tuesday.