Hewitt is Australia's all-time win leader with a 40-13 singles record and 14-3 mark in doubles. Kyrgios is 1-1 in his Davis Cup career, with the win coming in singles.
That mixture of experience and young player faces a formidable French team, which boasts a pair of Top 10 players for singles and Top 40 players in doubles for the best-of-five series.
Kyrgios is to meet world No. 9 Richard Gasquet in the series opener Friday before Hewitt plays 10th-ranked Jo-Wilfried Tsonga. Hewitt returns for a doubles match Saturday, teaming with Chris Guccione against French players Julien Benneteau and Gael Monfils, both of whom are ranked in the 30s in world singles.
Hewitt is to play Gasquet in the first match of Sunday's singles with Kyrgios drawing Tsonga in the fifth, and potentially deciding, match.
The Australia-France series is historic with the last two meetings deciding the Davis Cup champion. France won the title in 2001, beating Australia 3-2 in the final, and Australia won in 1999, edging France 3-2 in that year's championship series. Australia is 10-4 overall against France.
This weekend's series is to be played in La Roche sur Yon in western France. A red clay court has been installed for the matches.
The Australia-France winner draws either Spain or Germany in the April 4-6 Davis Cup quarterfinals.