Richard Gasquet will face Borna Coric in the opening singles of the Davis Cup semi-final between injury-hit France and hosts Croatia in Zadar.
Rising French star Lucas Pouille then takes on 2014 US Open champion Marin Cilic at the Kresimir Cosic Hall on Friday.
France has the clear advantage in doubles, with Nicolas Mahut and Pierre-Hugues Herbert - the top-ranked doubles players in the world - up against Ivan Dodig and Marin Draganja.
In reverse singles on Sunday, Gasquet faces Cilic and Pouille - a US Open quarter-finalist last month - takes on the 19-year-old Coric.
France is without its two best players, US Open semi-finalist Gael Monfils and Jo-Wilfried Tsonga.
Both are hampered by knee problems.
Monfils pulled out on Wednesday while Tsonga was replaced by Gasquet last week.
Gasquet has an 11-8 record in singles, while the inexperienced Pouille has played only one Davis Cup match - beating Jiri Vesely in the 3-1 quarter-final win against the Czech Republic.
But the 22-year-old Pouille will be full of confidence after knocking out 14-time Grand Slam champion Rafael Nadal in the fourth round of the US Open, where he then lost to Monfils in the quarter-finals.
For the Croats, Cilic is 19-9 overall in singles and Coric is 5-5.
Croatia beat the United States 3-2 in the quarter-finals, with the versatile Cilic also lining up in doubles with Dodig against the Bryan brothers.
France has won nine Davis Cup titles and lost eight finals, while Croatia won its only final 11 years ago away to Slovakia.
France, which is captained by 1983 French Open champion Yannick Noah, is also trying to curb a losing streak.
Since winning the title in 2001 against Australia, it has lost three finals - in 2002, 2010, and 2014.
The winner will play either defending champion Britain, led by three-time Grand Slam and two-time Olympic champion Andy Murray, or resurgent Juan Martin del Potro's Argentina in the final.
