Didier Deschamps' side have been drawn alongside Netherlands in Group 1 of League A, the two teams having faced off in World Cup qualifying, as well as the reigning world champions.
League B will see the Republic of Ireland meet Wales, now coached by Ryan Giggs, and Denmark, who beat the Irish in the play-off for the 2018 World Cup finals.
Scotland will take on Albania and Israel in the three-team Group 1 of League C, while Group 4 will see Serbia take on Montenegro.
UEFA's bold new competition aims to replace a large portion of friendlies with more competitive fixtures against similarly ranked teams.
The system will also offer an alternative route into the European Championship, beginning with Euro 2020.
Teams who finish top of their groups in League A will compete at the Nations League finals next year, while countries can also be promoted and relegated depending on the final standings.
The matches begin in September 2018.
England have been drawn with Spain and Croatia in the inaugural UEFA Nations League.