Roger Federer's final match will see him play alongside old rival Rafael Nadal in the Laver Cup doubles on Friday.
The pair will represent Team Europe against Team World's Jack Sock and Frances Tiafoe at London's O2 Arena.
Before that match, Andy Murray will start the evening session in singles against Alex de Minaur at 19:00 BST.
Federer, a 20-time Grand Slam winner, said last week he would retire at the team event, which starts on Friday.
The 41-year-old Swiss said it would be "wonderful" to play alongside Spaniard Nadal, 36, who has 22 major titles.
"I'm not sure if I can handle it all but I'll try," said Federer.
"I have had some tougher moments as well in the past, being horribly nervous all these years sometimes before matches. This one definitely feels a whole lot different.
"Of course, it's super special playing with Rafa. I'm happy to have him on my team and not playing against him."
Nadal said he was looking forward to an "unforgettable" match with his rival against the American duo.
"One of the most important, if not the most important player in my tennis career is leaving," the 36-year-old Spaniard said.
"At the end, this moment will be difficult. I'm super-excited and grateful to play with him."
Federer has struggled with a knee problem and does not feel able to play singles.
His last competitive match was a defeat by Poland's Hubert Hurkacz in last year's Wimbledon quarter-finals.