Petra Kvitova will take on Anastasia Pavlyuchenkova in the opening singles match of the Fed Cup final between the Czech Republic and Russia in Prague on Saturday.
World No 6 Kvitova, who has won 20 of her 22 singles matches in the team competition since 2011, is bidding to lead the Czech Republic to a fourth title in five years following their victories in 2011, 2012 and 2014.
The 26-year-old has a 6-2 record against Pavlyuchenkova, who will be hoping to set Russia on their way to their first Fed Cup success since 2008.
World No 4 Maria Sharapova, who is playing in her first Fed Cup final, will be up against Karolina Pliskova in the second singles on the indoor hard court at the O2 Arena.
Pliskova, whose only previous Fed Cup singles experience came earlier this year when she won twice against Canada in Quebec City, has been preferred to Lucie Safarova, who has a 9-1 singles record on home soil.
World No 11 Pliskova has been rewarded for her fine form this year which has seen her reach six finals.
In Sunday's reverse singles, Kvitova will first play Sharapova, then Pliskova will take on Pavlyuchenkova, while Safarova and Barbora Strycova will tackle Ekaterina Makarova and Elena Vesnina in the doubles.