Spain's Rafael Nadal has been drawn in an exciting group containing US Open champion Dominic Thiem as he looks to win a maiden ATP Finals title.
Greece's defending champion Stefanos Tsitsipas and in-form Russian Andrey Rublev make up the four-man group at next week's season-ending tournament.
World number one Novak Djokovic has been pitted against Russia's Daniil Medvedev, Germany's Alexander Zverev and Argentina's Diego Schwartzman.
The event starts in London on Sunday.
While 34-year-old Nadal aims to fill the biggest gap left in his illustrious trophy cabinet, Serbia's Djokovic is bidding for a record-equalling sixth ATP Finals title.
Victory would move him level with Swiss rival Roger Federer, who is not taking part after not playing since February because of a knee injury.
Taking place behind closed doors because of coronavirus restrictions, the tournament will be held for the 12th and final time at the O2 Arena before moving to Turin from 2022.
The round robin stage sees the players - who have qualified as the world's eight leading men on the ATP Tour in a truncated 2020 - face each other once, with the top two in each group going through to the semi-finals on Saturday, 21 November.
The finals - singles and doubles - will be held on Sunday, 22 November.
The doubles draw will be held once the final spot has been decided, with Britain's Jamie Murray and Neal Skupski still in the running.