Galthie, who replaced Jacques Brunel as head coach after the Rugby World Cup, has selected back-row Ollivon to lead the side after Guilhem Guirado's retirement from international rugby.
Toulon's Ollivon only has 11 caps to his name but is set to skipper his country when it faces England in its first match of the tournament on 3 February (AEDT).
"It's an honour to be captain of the France team," Ollivon said.
"It's a somewhat special moment, quite moving. I can't wait to start the adventure."
Galthie has put his faith in youth, with 20-year-olds Louis Carbonel, Jean-Baptiste Gros and Killian Geraci among those called up to a squad with an average age of 24.
Wing Teddy Thomas is recalled after being overlooked for the Rugby World Cup in Japan, but there is no place for the likes of Maxime Medard and Yoann Huget.
Forwards: Dorian Aldegheri, Cyril Baille, Demba Bamba, Camille Chat, Anthony Etrillard, Jean-Baptiste Gros, Mohamed Haouas, Julien Marchand, Jefferson Poirot, Cyril Cazeaux, Killian Geraci, Bernard Le Roux, Boris Palu, Romain Taofifenua, Paul Willemse, Gregory Alldritt, Charles Ollivon, Dylan Cretin, Francois Cros, Alexandre Fischer, Sekou Macalou, Selevasio Tolofua, Cameron Woki.
Backs: Antoine Dupont, Baptiste Serin, Maxime Lucu, Romain Ntamack, Louis Carbonel, Mathieu Jalibert, Gael Fickou, Virimi Vakatawa, Arthur Vincent, Julien Heriteau, Gervais Cordin, Lester Etien, Gabriel Ngandebe, Damian Penaud, Vincent Rattez, Teddy Thomas, Anthony Bouthier, Kylan Hamdaoui, Thomas Ramos.