The Spain international scored the winning goal as City lifted the trophy for the first time when they beat Inter Milan 1-0 in Saturday's final.
Rodri appeared in all but one of City's Champions League matches, scoring twice. He delivered a standout performance in the final, earning the Player of the Match award.
Napoli's Khvicha Kvaratskhelia (22) was named the Champions League's Young Player of the Season, capping a remarkable campaign for the Georgian.
Kvaratskhelia won the league title with Napoli and also claimed Serie A's Player of the Season award earlier this month.
Team of the season
Goalkeeper: Thibaut Courtois (Real Madrid)
Defenders: Kyle Walker (Man City), Ruben Dias (Man City), Alessandro Bastoni (Inter), Federico Dimarco (Inter)
Midfielders: John Stones (Man City), Kevin De Bruyne (Man City), Rodri (Man City)
Forwards: Bernardo Silva (Man City), Erling Haaland (Man City), Vinicius Junior (Real Madrid)
