Valencia have asked the Royal Spanish Football Federation (RFEF) if Marcelino is eligible to coach the team following the sacking of Pako Ayestaran, according to reports.
Ayestaran was dismissed on Tuesday after the club's fourth defeat in as many La Liga games over the weekend.
Valencia-based newspaper Superdeporte has reported that Los Che sporting director Jesus Garcia Pitarch is considering handing the reins to Marcelino.
The 51-year-old Marcelino, who took charge of Villarreal in 2013 and led the club to a fourth-place finish in La Liga last season, was surprisingly dismissed by the club on Aug. 10.
The chances of seeing him at the helm of Valencia this season are slim, says AS, as according to article 162 of the RFEF rules, a manager is not allowed to coach a team in the same division if he has previously led another side in that same campaign.
Marcelino did not manage Villarreal in an official game in the 2016-17 season before his dismissal, but according to rules, the official start of the campaign was on July 1.
AS reports that Marcelino has already asked the RFEF about the possibility of coaching another La Liga side this season.
A poll by Superdeporte asked Valencia fans which coach they would like to see in charge and the most popular response, by a big margin, was Marcelino, who received 48 percent of the vote.
Valencia interim coach Salvador Gonzalez "Voro" is hopeful that the club will bring in the right man.
"Every coach has different characteristics," Voro told Superdeporte. "Some better than others and we cannot measure a coach just because of his profile but on the whole.
"My wish is that the club gets it right. There is still a long way to go in La Liga for the team to come out of this situation and for the fans to be happy."
Valencia are currently bottom of the La Liga table and host Alaves on Thursday, before travelling to Leganes three days later.