Cristian Zapata will miss Villarreal's Champions League tie against Manchester City with a sprained knee.
The Colombian defender, who sustained the problem at the weekend, will be out of action for around five weeks.
He has joined an injury list for the Yellow Submarine which includes Cani, Marcos Senna and Marco Ruben.
Striker Giuseppe Rossi will also miss Wednesday's fixture against City, having undergone surgery to correct a knee ligament injury that he suffered against Real Madrid last week.
A stoppage time goal from Sergio Aguero sealed the victory for City when the two sides met at the Etihad Stadium a fortnight ago.