Opening the Men's Singles event, UK's Andy Murray took his first step in defending his title, ousting Belgium's David Goffin 6-1, 6-4, 7-5.
Wimbledon is Murray's first event since picking up former women's world number one Amelie Mauresmo as his new coach.
Following his first-round victory, Murray spoke to the media about how Mauresmo helped him relax coming into the match.
"One of the things she said was that she tried to take in the atmosphere and the experience of walking out on the court as defending champion, you never know if you will get the chance to do that again. She has quite clear memories doing that herself, so this is one of the things she told me to try and do."
Following on the heels of Murray's victory, Chinese world number-2 Li Na opened her tournament against Poland's Paula Kania, currently ranked as world's number 183.
Despite the pressure of qualifying for her first major, and playing on center court, the 22-year old Kania showed poise, jumping out to an early lead and breaking Li Na's serve.
However, the veteran Li turned her game around, eventually downing Kania 7-5, 6-2.
Speaking to reporters after the match, Li Na admits Wimbledon isn't her strongest event.
"I never think I can play well on the grass court. Because for me, it's tough. I think it is tough for everyone because for the whole year you can only play on the grass court for a short period of time. Also we can not do training on the grass. It is pretty close to the French Open, only two weeks apart. To change the surface in such a short time is very tough for me."
Li Na is now set to take on Austrian veteran and world number-38 Yvonne Meusberger in Round-2.
Rising Chinese star Peng Shuai is also through to round 2 after getting past a British qualifier in 3-sets.
Also opening his tournament on center court was men's world number-2 Novak Djokovic, who has cruised into the 2nd round with a decisive 6-love, 6-1, 6-4 thrashing of Kazakhstan's Andrey Golubev.
But while most of the big names did make it through the first day, there were a few seeds who fell on both the men's and women's draws on day one, including American Sloane Stephens, Australian Sam Stosur, Spain's Fernando Verdasco and Italy's Andreas Seppi.
For CRI, I'm Duan Xuelian, reporting from Wimbledon.
