Britain's Laura Robson is confident she can pull off the shock result of the tournament by beating former champion Maria Sharapova.
The Londoner, 17, is scheduled third on Court One for Thursday's second-round match against the fifth seed.
Elena Baltacha is the other Briton in action, and she plays Shuai Peng of China in the fourth match on Court Two.
Roger Federer will hope to continue his fine form on Centre Court when he plays Adrian Mannarino of France.
The six-time champion is expected to have little difficulty against the world number 55, who enjoyed a good run at Queen's Club earlier this month before losing to Britain's James Ward in the quarter-finals.
The Swiss third seed, chasing a 17th Grand Slam title, will follow Li Na on to Centre, with the French Open champion facing Sabine Lisicki of Germany.
But all eyes will be on Court One when Robson takes to the turf for a daunting task against Sharapova, one of the favourites for the women's title after she brilliantly dispatched of Anna Chakvetadze in straight sets on Tuesday.
Robson was playing in an under-12 tournament in Edinburgh when a then 17-year-old Sharapova became a world star by winning at SW19 back in 2004.
However, the Briton refuses to be overawed, with victory over Angelique Kerber on Wednesday - her maiden Grand Slam success - boosting the 2008 Junior Wimbledon champion's confidence.
"You've got to be confident going into these matches," said the world number 254, who has struggled with form and fitness this season.
"Hopefully I can play as well as I know I can. It's a really important game so I'll have to get some rest, refocus and think of a new game plan.
"I'm going to be on Court One playing against Sharapova, so I think that's pretty special."