Villarreal have suspended defender Ruben Semedo without pay after he was arrested and charged with attempted murder and robbery.
The 23-year-old Semedo also faces charges of assault, illegal detention and illegal possession of firearms.
Semedo was accused of tying up, assaulting and threatening another man in an incident last week. Authorities said he and two other men allegedly held the victim captive while they robbed his apartment.
Villarreal said on Friday they were dismayed by the seriousness of the charges against Semedo and, although they respected "the presumption of innocence," they would suspend the player until the end of the legal process.
Semedo, who is Portuguese, testified before a judge in the southeastern city of Lliria on Thursday and was led from the court in handcuffs.
Semedo's agents told Spanish media the player denies any wrongdoing.
Villarreal signed the former Portugal under-21 international from Sporting Lisbon last summer for a reported fee of €14 million.