The 40 year old has walked out on the club at their training camp in the United States, apparently bringing to an end his association with Los Che
The 40 year old had already announced his departure at the end of the season, but accompanied the club on their end-of-season tour of the States, at the insistence of president Manuel Llorente.
The report states that because Emery's contract runs until June 30, he was contractually bound to travel with the team.
However, the former Almeria boss asked to leave after Valencia secured a 1-0 friendly victory over Portland Timbers on Wednesday evening amid rumours of disagreements with the board.
Emery, who has already accepted an offer to coach Spartak Moscow next season, was reported to have become disillusioned, and asked to leave the camp on 'personal grounds', giving up the opportunity to lead Los Che for the final time against Houston Dynamo on May 31.
Instead, Juan Carlos Carcedo and assistant Juanjo Vila will now lead the side against Houston, before Mauricio Pellegrino takes up the reins at Mestalla this summer.
Valencia finished the Liga season in third place, and have qualified for the Champions League group stage.