The teams for the match in Belgrade, which begins on November 15, were announced on Tuesday.
Djokovic is joined by Janko Tipsarevic, who is battling to recover in time from a heel injury, Nenad Zimonjic and Ilija Bozoljac, with the latter two expected to be the doubles pair.
Viktor Troicki, who won the decisive rubber in Serbia's first Davis Cup title in 2010, is currently serving an 18-month ban for a doping offence and is still waiting on the verdict of his appeal to the Court of Arbitration for Sport, which could come any day.
The Czechs upset reigning champions Spain 12 months ago and they have named three of the same four players in their side for this year's final.
Tomas Berdych and Radek Stepanek, who scored all the points 12 months ago, are again joined by Lukas Rosol while Jan Hajek completes their line-up.