The world number one will be in action on clay in Belgrade only four days after losing the US Open final to Rafael Nadal in New York.
Djokovic plays the opening rubber against Canada's Vasek Pospisil, with Janko Tipsarevic facing Milos Raonic in the second singles match.
Helping Serbia win the Davis Cup for the first time in 2010 proved a major catalyst for Djokovic's fantastic season in 2011, where he won three grand slam titles and became world number one.
The 26-year-old told reporters: "It's not the first time I've had just two days to get ready for the Davis Cup after long-haul flights.
"I am tired and jet-lagged as I couldn't get here before Wednesday, but I am fit now and we haven't played at home in the Davis Cup for two years. Hence I am as motivated and inspired as ever to play for my country in this team event."
The other semi-final pits reigning champions Czech Republic against Argentina in Prague.
It is the second year in a row that the sides have met at this stage, with the Czechs handing Argentina a rare home defeat 12 months ago.
Radek Stepanek was the Czech hero in last year's final and he plays the first rubber against Juan Monaco before Tomas Berdych takes on Leonardo Mayer.
Argentina captain Martin Jaite said: "Tennis always gives you a chance for revenge. We lost a tough semi-final last year but we are very happy to be again in the semi-finals and we are happy to be in Prague.
"We have to play very, very well. We play the defending champions, a great team."
The O2 Arena was the venue for the Czechs' victory over Spain in the final, and Berdych said: "The arena feels great and we will try to do our best and continue this winning streak here in Prague.
"We thought it would be Mayer playing the second singles. His game is suited to these courts. I saw some of his match against Andy Murray at the US Open and he played well."
There are also eight World Group play-offs taking place this weekend, with Nadal returning to the Spain team for their match against Ukraine in Madrid.
The US Open champion will face Sergiy Stakhovsky in the second rubber after Fernando Verdasco has taken on Alexandr Dolgopolov.
Stakhovsky upset Roger Federer at Wimbledon but beating Nadal on clay is another matter, even though the world number two has had minimal time to prepare.
Spain have not played a match outside the World Group for 17 years, and Nadal said: "I arrived a little bit tired after what happened in New York but I hope to be ready for the confrontation.
"It is always a challenge to change surface in a very short period of time but it is something that has happened in the past to me and I hope to adapt my game to be competitive.
"I have to try because I feel that it is a very important confrontation for us to stay in the World Group."