In addition to the domestic league, Villarreal participated in this season's editions of the Copa del Rey, the UEFA Champions League, and the UEFA Super Cup.

Note: Flags indicate national team as defined under FIFA eligibility rules; some limited exceptions apply.

Note: Flags indicate national team as defined under FIFA eligibility rules; some limited exceptions apply.

Note: Flags indicate national team as defined under FIFA eligibility rules; some limited exceptions apply.

[32][33] The draw for the group stage was held on 26 August 2021.