Rafael Nadal will continue his quest to complete a calendar Grand Slam, while Katie Boulter is the headline act for Great Britain on day four at Wimbledon.
Nadal has already clinched the Australian and French Open crowns this season and is aiming to claim his first Wimbledon title since 2010.
The Spaniard, 36, takes on Lithuania's Ricardas Berankis in round two.
Boulter, though, will be first out on Centre Court on Thursday when she faces Czech sixth seed Karolina Pliskova.
The 25-year-old world number 118 is looking to reach the third round at the All England Club for the first time.
Boulter will have to overcome a player who reached last year's final to do so, but she has the confidence of beating Pliskova at Eastbourne last week.
Harriet Dart is also in action, while fellow Britons Liam Broady, Jack Draper and Alastair Gray compete in the men's draw.
Broady takes on Argentine 12th seed Diego Schwartzman, with Draper last on Court One against Australian 19th seed Alex de Minaur and Gray facing American 11th seed Taylor Fritz.
Dart, who stormed through her first-round match on Wednesday, is straight back out to take on American eighth seed Jessica Pegula.
Heather Watson will resume her second-round match against Wang Qiang after darkness forced it to be suspended on Tuesday with the Briton leading 7-5 5-4, having being broken when she served for the match.
'Every victory helps'
Nadal has won 22 Grand Slam titles, but never has he claimed all four of the sport's major prizes in the same year - going closest in 2010 when he won at Roland Garros, Wimbledon and Flushing Meadows after being knocked out in the quarter-finals in Melbourne.
He has the opportunity to better that this year after winning the first two Slams of the season, with the US Open to follow after Wimbledon.
Nadal told reporters he had not played on grass in three years after a first-round victory over Argentine Francisco Cerundolo that went to four sets and was trickier than the two-time Wimbledon champion might have anticipated.
"Every victory helps," said Nadal. "I spent a long time on court. I really hope that will help.
"I need to keep improving things, but at the end of the match I improved. At the most critical moment, I think I raise my level. That's a very positive thing.
"[I need to] be ready for Ricardas in the second round, be another day, be humble enough to accept the challenge and accept that the situation will not be perfect for the moment.
"But with the things I have, I need to find a way to keep going. Because every day that I am able to survive, there is a much bigger chance that I start playing at much higher level."
Kyrgios drama continues
The racquet-wielding soap opera that is Nick Kyrgios will also return on Thursday after an incident-packed first-round win over British wildcard Paul Jubb.
The Australian has the ability to amaze with his tennis, but it was his other on-court antics that caused a stir during that victory, admitting afterwards that he spat in the direction of a "disrespectful" fan.
"I would not be doing that to someone who was supporting me," he said. "I've been dealing with hate and negativity for a long time, so I don't feel like I owed that person anything.
"Like, he literally came to the match to not even support anyone really, it was more just to stir up and disrespect. That's fine. But if I give it back to you, then that's just how it is."
The 27-year-old world number 40, who reached the quarter-finals at SW19 in 2014, faces Serbia's 26th seed Filip Krajinovic.
Coco Gauff, the American 11th seed, completes the Centre Court line-up against Romania's Mihaela Buzarnescu, while Polish top seed Iga Swiatek is pitted against Lesley Pattinama Kerkhove of the Netherlands on Court One.
In the men's draw, Greek fourth seed Stefanos Tsitsipas faces Australian Jordan Thompson and Spain's Roberto Bautista Agut, the 17th seed, meets Colombian Daniel Galan.