Serbia's Novak Djokovic will face Radek Stepanek of holders the Czech Republic in the opening rubber of the Davis Cup final starting on Friday, following Thursday's draw.
Djokovic, the world number two, will face 44th-ranked Stepanek on the hardcourt surface at the Belgrade Arena at 1500 GMT on Friday.
In the second rubber, 117th-ranked Dusan Lajovic of Serbia will take on world number seven Tomas Berdych.
Lajovic has replaced Janko Tipsarevic, the world number 36, who has been ruled out with a heel injury. Serbia also miss 76th-ranked Viktor Troicki due to a doping ban.
"Obviously it's a handicap for our team that we don't have Viktor and Janko now," Djokovic said before describing Lajovic as "a young and talented player" who can "play on a high level."
"In the Davis Cup final with 17 or 18,000 people supporting him it's normal to expect that he can deliver his best," said Djokovic.
Lajovic, who has lost all four ATP rubbers he has played this year, insisted he was ready to surprise.
"I'm very excited, I was working hard for this and I'll give my best," said the 23-year-old.
Meamwhile, Berdych admitted he did not know much about his rival, saying: "I will try to do some small scouting about him (but) we came here to try to score three points during the weekend and the plan stays the same."
Fresh from triumphing in the ATP Tour Finals, Djokovic said he was tired but added "the fact that I've won over 20 matches in a row can give me positive energy and confidence.
"I hope that I can of course contribute to the first point and to the first victory. That would mean a lot... of course that releases the pressure from the second player," he said.
"Obviously playing for Serbia and playing the Davis Cup final gets the last drop of energy and motivation out of me."
Stepanek said nobody expected him to win, which might be an advantage.
"Everybody expects Novak to win the first point for Serbia. This may open my wings," he said, vowing to "look for small gaps in his game."
In Saturday's doubles, Serbia's Ilija Bozoljac and Nenad Zimonjic are due to face the Czech Republic's Jan Hajek and Lukas Rosol.
But the Czechs are almost certain to bet on Berdych and Stepanek for the doubles too as the two have lost only one of their 14 Davis Cup doubles rubbers together since teaming up in 2007.
"We'll see after Friday but everything is possible," said Vladimir Safarik, the interim Czech captain who has replaced Jaroslav Navratil, down with a pulmonary embolism.
Serbia captain Bogdan Obradovic said he might use Djokovic in the doubles rubber.
"This is a serious situation, every point in this tie is important and we have opened all the options. Nenad is able to play with any player here, he's got the ability to adapt to every player," he said.
In Sunday's reverse singles, Djokovic will face Berdych and Lajovic will then take on Stepanek.
The Czech Republic and Serbia last clashed in the 2012 quarter-finals, with the Czechs winning 4-1 in Prague.
Two years earlier, Serbia had beaten the Czechs in the semi-finals in Belgrade 3-2.
Serbia won their only Davis Cup title in 2010, beating France 3-2 in Belgrade.
The Czechs, playing their third final in five years, lifted the trophy last year after downing Spain 3-2 in Prague.
Previously, Czechoslovakia, which split into the Czech Republic and Slovakia in 1993, won the title in 1980.