Nick Kyrgios will attempt to reach a first Grand Slam singles quarter-final since 2015 when he opens play on Wimbledon's Centre Court on Monday.
Kyrgios will face American 20-year-old Brandon Nakashima in the fourth round.
Later on Monday, two-time champion Rafael Nadal plays the Netherlands' Botic van de Zandschulp last on Centre.
Completing the Centre Court line-up, Nadal's compatriot Paula Badosa will be in action after Kyrgios, facing 2019 champion Simona Halep.
Last on Court One, Harmony Tan takes on 20th seed Amanda Anisimova on a calmer than usual second Monday at Wimbledon.
Previously, all fourth-round matches were played on the second Monday but the introduction of play on middle Sunday means the fourth round is now split over two days.
'I'm actually one of most liked' - Kyrgios
Kyrgios has drawn crowds at this year's Wimbledon as he offers ongoing commentary on his, and sometimes the umpire's, performance during matches.
For the events and antics in Saturday's third-round match, Kyrgios was fined $4,000 (£3,300) for an audible obscenity while Tsitsipas must pay $10,000 (£8,250) for unsportsmanlike conduct.
It remains to be seen whether the 27-year-old Kyrgios' fourth-round match against Nakashima will reach boiling point too.
Nakashima is ranked 56th in the world - 16 places below Kyrgios - and had never made it past the first round of Wimbledon before this year having played in the tournament for the first time in 2021.
The American beat 13th seed Denis Shapovalov in the second round, but Kyrgios on Centre Court presents a big step up.
Following his victory against Tsitsipas, Kyrgios told reporters that his on-court behaviour was not causing any issues among other players, saying: "I'm good in the locker room. I've got many friends, just to let you know. I'm actually one of the most liked."
Asked what had stopped him going further than a Grand Slam singles quarter-final in his career so far, Kyrgios added: "I haven't been able to play a consistent level of tennis.
"I'm very accountable. I haven't been able to produce my best tennis a consistent number of times in the year, and that's that simple."
Nadal must stay 'aggressive'
Along with top seed Novak Djokovic, Nadal is the only player left in the men's draw who has reached a Grand Slam singles semi-final before.
The Spaniard is making his first appearance at Wimbledon since 2019 because of a recurring foot injury and is playing his first grass-court matches since then.
But the 36-year-old looked comfortable in a straight-set victory against Lorenzo Sonego in the third round having dropped a set in each of the previous two rounds.
Nadal faced Van de Zandschulp, seeded 21st at Wimbledon, en route to winning his 14th French Open title in June and beat the Dutchman in straight sets.
But Nadal said his opponent has been "improving unbelievably the last year", adding: "It was a good challenge in the French and I think he will be more [at Wimbledon].
"He's a complete player with a lot of great things and I need to keep going the way that I played [against Sonego] - playing aggressive and playing with the right energy."
In Monday's other fourth-round men's matches, American 11th seed Taylor Fritz faces Australian qualifier Jason Kubler second on Court One, while Kubler's compatriot Alex de Minaur plays Chile's Cristian Garin first on court two.
Tan's opponent could reach final - Gauff
France's Tan has top billing on Court One after an impressive run to the fourth round which has included victories over Serena Williams and Britain's Katie Boulter.
The world number 115 has been playing tennis beyond her ranking and now faces 20th seed Anisimova, who was praised by Coco Gauff after she came from a set down to beat her fellow American in the third round.
"I think she has a good shot of going all the way to the final," Gauff said.
"If she plays like she did those last two sets against me, I think that's some top-notch tennis right there."
Kazakhstan's 17th seed Elena Rybakina will open the day on Court One against Croatian world number 80 Petra Martic.
France's Alize Cornet and Australia's Ajla Tomljanovic complete the women's line-up and they play second on court two.