Kai Havertz, Timo Werner and Hakim Ziyech lead the attack. Toni Rudiger makes his 150th Chelsea appearance in defence.
In midfield, Mateo Kovacic, twice a winner of the Super Cup when at Real Madrid, lines up alongside N’Golo Kante who again skippers the side.
The players who featured in the latter stages of the Euros plus Thiago Silva are added to the bench.
Chelsea: Mendy; Zouma, Chalobah, Rudiger; Hudson-Odoi, Kante (c), Kovacic, Alonso; Ziyech, Havertz, Werner.
Villarreal: Asenjo; Foyth, Albiol (c), P Torres, Pedraza; Trigueros, Capoue, A Moreno; Pino, G Moreno, Dia.
Subs: Rulli, Gaspar, Morlanes, Alcacer, Iborra, Estupinan, Barreno, Raba, Pena, Mandi, Gomez, Nino.
The referee is Sergei Karasev from Russia.