In the other singles match announced Thursday, Janko Tipsarevic will face Milos Raonic, Canada’s top player.
The doubles will be played Saturday and reverse singles are Sunday in Belgrade.
Djokovic says he hopes to recover from the jet leg after losing the U.S. Open final to Rafael Nadal on Monday in New York.
Canada has never made it this far in the Davis Cup, while Serbia won the event in 2010.
The winner will face either the Czech Republic of Argentina in the final in November.
Source: Associated Press