The 24-year-old world number three will also take on Spaniard David Ferrer – who he beat in the Australian Open semi-finals earlier this year – and Tomas Berdych of the Czech Republic in Group A.
The latter provides a chance for revenge for Murray, after Berdych ended the Briton’s 18-match winning run at the Paris Masters last week.
Rafael Nadal is the top seed in Group B alongside Roger Federer – who won a record-equalling fifth circuit finale title in London last year – plus Jo-Wilfried Tsonga of France and American Mardy Fish.
Djokovic has had a stunning season which has seen him claim the Australian Open, Wimbledon and US Open titles among a total of 10 tour successes, however he is struggling at present with a shoulder problem which forced him to withdraw from the Paris Masters last week.
The first singles match will be Federer v Tsonga on Sunday, a repeat of the Paris Masters final. Nadal will take on Fish on Sunday night. Murray begins his campaign against Ferrer, while Djokovic takes on Berdych later in the day.
The tournament runs until Sunday, November 27.