Both top seeds will be in action on Centre Court on the opening day of Wimbledon.
As defending champion, Novak Djokovic was always going to open up play on the main court at 1300 BST. He faces former world number one Juan Carlos Ferrero.
However, organisers have also opted to put ladies' top seed Maria Sharapova on Centre. The French Open champion will face Australia's Anastasia Rodionova after the Djokovic match.
The third and final match of the day on Centre will be one of the highlights of the first round, 2010 finalist Tomas Berdych against the ever-dangerous Latvian, Ernests Gulbis.
Another of the marquee first-round matches will open proceedings on Court One, namely Queen's Club bad boy and runner-up David Nalbandian against eighth seed Janko Tipsarevic.
Third seed Roger Federer will then take on Spain's Albert Ramos before Kim Clijsters, playing her final Wimbledon tournament, faces former world number one Jelena Jankovic in the pick of the ladies' opening-round matches.
Five Britons will be in the singles action on Monday.
Heather Watson will fancy her chances of upsetting Iveta Benesova, who does not like the grasscourts.
Plenty of eyes will also be on Johanna Konta, the Australia-born player who recently swicthed her allegiance to Great Britain. She takes on 28th seed Christina McHale, while Naomi Broady plays Lourdes Dominguez Lino.
In the men's singles, US Open junior champion Oli Golding will make his senior Wimbledon debut on Court Two against Russia's Igor Andreev.
Five-time champion and third seed Agnieszka Radwanska will also grace that court.
Josh Goodall is the other Briton playing on Monday, with Andy Murray due to make his first appearance of the tournament on Tuesday.
In a change from previous years, play on the outside courts will get under way at 1130 BST. The first match on Centre and One will still be at 1300.