French Open champion Rafael Nadal of Spain will meet great rival Roger Federer of Switzerland, who comes into the week-long event on the back of tournament victories in Basel and Paris. (Also read: Paes-Bhupathi, Bopanna-Qureshi drawn in different groups)
Group B also features Paris finalist Jo-Wilfried Tsonga and American Mardy Fish.
Nadal and Federer meet in a repeat of the 2011 French Open final, the Swiss superstar's only Grand Slam final appearance of the season.
The 30-year-old comes into this tournament fresh from victory in Paris however, and can surpass Ivan Lendl and Pete Sampras with a sixth finals title with victory in London.
In Group A Britain's Andy Murray will face world number one Novak Djokovic in the group stages of the ATP World Tour Finals, following Tuesday's draw in London.
Murray, the winner of five tour titles this season, was also drawn in the same group as Spaniard David Ferrer and Czech Tomas Berdych, who knocked him out at the quarter-final stage of the Paris Masters last week.
Djokovic has won three of this season's four Grand Slam tournaments, including the Australian Open where he beat Murray in the final.
The Serb, who went on to win Wimbledon in the summer, has been struggling with back and shoulder injuries since his victory at the US Open in September.
Djokovic was forced to withdraw from the Paris Masters last week before the quarter-finals stage, although he is hopeful of being fully fit to compete in London.
The tournament begins Sunday and ends November 27.
Draw for the ATP Finals to be held in London:
Group A: Novak Djokovic (SRB), Andy Murray (GBR), David Ferrer (ESP), Tomas Berdych (CZE)
Group B: Rafael Nadal (ESP), Roger Federer (SUI), Jo-Wilfried Tsonga (FRA), Mardy Fish (USA)