Serbia's Janko Tipsarevic and France's Gael Monfils will face off in the opening match of the Davis Cup final in Belgrade on Friday.
The draw for the five matches was announced on Thursday, which also pitted world number three Novak Djokovic against Gilles Simon in the second singles rubber on Friday.
Serb Viktor Troicki was edged out by Tipsarevic for the second singles spot behind Djokovic, but has been named to join Nenad Zimonjic to play Frenchmen Arnaud Clement and Michael Llodra in the doubles on Saturday.
Djokovic will face Monfils, and Tipsarevic will face off against Simon in the reverse singles fixtures on Sunday.
Monfils began the mind games on Thursday leading into the final, stating Tipsarevic will be tentative in front of his boisterous home fans.
"I know Janko. He will be very nervous because he plans to come out first on the court in front of the Serbian crowd. It will be tough for him. I will try to be very relaxed and just play my game," Monfils said.
France captain Guy Forget was forced to decide between Simon and Llodra for the second singles spot, and he opted against picking the in-form Llodra to face his recent victim in Djokovic.
"It's always a tough choice to choose someone because you let someone down. I expect Gilles to play a great match against Novak. I expect Michael to play great doubles with Arnaud (Clement). They've done so many times in the past," Forget said.
Djokovic said the draw was predictable, and the World Tour Finals semi-finalist in London last week will aim to bring his recent form into the Cup finale.
"That's what we kind of expected (of the draw). Regardless of who I play, I have to be on top of my game," Djokovic said.
"It's the finals of Davis Cup. Everybody will try to perform their best and everybody will have a lot of motivation to play great tennis in these three days."