Lucie Safarova of holders Czech Republic will take on Serbia's Ana Ivanovic in the first singles rubber of the Fed Cup final here on Saturday, after Friday's draw.
Safarova, the world number 17 and Czech number two, will face world number 12 Ivanovic, who is Serbia's number one, in Prague's O2 Arena from 1230 GMT on Saturday.
Czech number one Petra Kvitova and Serbia's number two Jelena Jankovic will play the second singles tie on Saturday.
On Sunday, world number eight Kvitova will face Ivanovic, before Safarova plays Jankovic, 22nd in the world, in the final singles tie.
The Czech Republic's Andrea Hlavackova and Lucie Hradecka are then due to face Serbia's Bojana Jovanovic and Aleksandra Krunic in the closing doubles rubber, but the teams may change.
Hosts Czech Republic are defending the trophy after they beat Russia in Moscow 3-2 in 2011.
Former Czechoslovakia, which split peacefully into the Czech Republic and Slovakia in 1993, lifted the Fed Cup five times between 1975 and 1988.
Serbia are playing their first Fed Cup final.