Tomas Berdych of the Czech Republic will play Viktor Troicki of Serbia in the opening singles match of the Davis Cup quarterfinals.
Radek Stepanek will face Janko Tipsarevic of Serbia in the second singles match on Friday on the indoor clay-court at O2 Arena.
Czech pair Frantisek Cermak and Lukas Rosol have been selected to play Ilija Bozoljac and Nenad Zimonjic in Saturday's doubles, but captain Jaroslav Navratil is expected to bring in Berdych and Stepanek. Changes are also possible for the Serbian pair.
The winner of the best-of-five series will face Argentina or Croatia in September's semi-finals.
The Serbian team is missing top-ranked Novak Djokovic.