Marcelino is set to take charge of Valencia.
Los Che confirmed the new coaching appointment on Thursday.
He will replace Voro and sign a two year deal, with the presentation set to take place after this season's league campaign has concluded.
Marcelino was sacked by Villarreal in August 2016 and has not worked since.
Voro took over after Cesare Prandelli walked out in December, following Pako Ayestaran, Gary Neville and Nuno Espirito Santo out of the door at Mestalla in the past two years.