The Czech Republic's Radek Stepanek and Spain's David Ferrer will open the action at the Davis Cup final here, following Thursday's draw.
Ferrer, the world number five and Spain's top player in Prague, will face 37th-ranked Stepanek at 4:00 pm (1500 GMT) on Friday on the hardcourt of Prague's O2 Arena.
After that meeting, world number six and Czech number one Tomas Berdych will take on Spain's Nicolas Almagro, the world number 11.
"I prefer David to start because of his experience," Spain captain Alex Corretja told reporters. "He has played more finals" than Almagro."
Ferrer, who has won six out of his nine games against Stepanek, predicted a tough tie, similar to their five-setter in 2009 when Spain thrashed the Czechs 5-0 in the Davis Cup finals.
"It was an amazing match and this time it's going to be similar. I'll have to play my best tennis to beat him," said the 30-year-old Ferrer.
Spain have won three Davis Cup trophies in the last four years, and they also won the competition in 2000 and 2004.
Czechoslovakia, which split peacefully into the Czech Republic and Slovakia in 1993, won the Davis Cup in 1980 with a team led by the then 20-year-old Ivan Lendl.
Stepanek said he might ask Lendl for advice before the game with Ferrer as Lendl coaches Andy Murray, whose encounters with the Spaniard are more frequent.
"I might have a question. But I have played an awful lot of games against Ferrer," Stepanek said.
"I know Ferrer is a big fighter, you really have to earn your points against him," he added.
As if to retaliate for the heavy clay chosen by Spain for the 2009 finals in Barcelona, the Czechs have opted for a superfast Novacrylic Ultracushion hardcourt.
Ferrer admitted earlier this week he was not very happy with the court, but then decided Spain had "a very good team to play very good tennis on this type of surface."
The 33-year-old Stepanek was more enthusiastic.
"I will try to use the surface to play my aggressive tennis," he said.
"It's our second final against the same rival in different conditions, we will want to make this work to our advantage."
Berdych said the game might be less demanding on a hardcourt than on clay, but added that the fast-serving Almagro might benefit from the surface too.
"He has a few weapons that can be unpleasant on this surface, including his serve," he said.
"The rubber will be terribly hard," said Berdych, adding that he was looking forward to playing in front of a crowd of almost 14,000.
"The crowds are an unofficial part of the team and they always help us a lot. This is why you play tennis," said Berdych, who has so far beaten Almagro eight times in 11 encounters.
Two weeks ago, the arena cheered on the Czech women's team to a successful Fed Cup defence against Serbia, and a Davis Cup win would give the Czechs a rare team double -- last achieved by the United States in 1990.
But Berdych, who is 27, said he would not draw inspiration from the women's team.
"When we made the team with Radek some years ago, our goal was to win the trophy again. Now it's our second attempt and we're at home and I don't think we need any inspiration," he said.
In Saturday's doubles, Czechs Lukas Rosol and Ivo Minar are due to face ATP Tour Finals winners Marcel Granollers and Marc Lopez.
But the Czech team is likely to make a change and rely on Berdych and Stepanek instead, a step often taken since the two formed the team in 2007.
Czech coach Jaroslav Navratil said the draw would give veteran Stepanek more rest before Saturday.
Besides he added, his opener on Friday "is important for Saturday's doubles -- if you're playing singles, it's much better than practising."
On Sunday, Berdych will face Ferrer before Stepanek takes on Almagro to round off the 100th edition of the Davis Cup final.
Draw for the Davis Cup final tie between the Czech Republic and Spain in Prague, starting on Friday:
Friday (from 1500 GMT)
Radek Stepanek (CZE) v David Ferrer (ESP)
Tomas Berdych (CZE) v Nicolas Almagro (ESP)
Saturday (from 1300 GMT)
Lukas Rosol, Ivo Minar (CZE) v Marcel Granollers, Marc Lopez (ESP)
Sunday (from 1200 GMT)
Tomas Berdych (CZE) v David Ferrer (ESP)
Radek Stepanek (CZE) v Nicolas Almagro (ESP)