Sevilla had earlier missed the chance to take top spot after a first-half Aritz Aduriz volley condemned them to a 1-0 defeat at Athletic Bilbao.
It was not a pretty performance from Valencia but they were determined in defence and Mustafi also showed his threat in attack as Nuno Espirito Santo’s side moved into second place, a point off Real, with 23 points from 10 games.
Luck was on their side when Manuel Trigueros slid in to clear a Sofiane Feghouli cross and ended up putting the ball past his own goalkeeper after six minutes to give Valencia the lead.
Villarreal pressed forward looking for the equaliser but while they moved the ball around well they were missing the killer touch in the final third of the pitch.
Instead, midway through the second half, Mustafi headed home a Pablo Piatti cross and then minutes later in another foray forward for a corner he slotted home on the volley.
As Valencia sat back on their lead, Trigueros pulled a goal back at the death for Villarreal.
“The table isn’t so important at the moment as we have only played 10 games,” Nuno told a news conference.
“We are playing well but there is a long way to go. If we want to be in the Champions League we will have to pick up a lot of points because the Spanish league is very strong. It means we will have to work hard to achieve it.”
Athletic’s La Liga form has suffered as they have struggled with the extra demands of Champions League football but they came out on top against Sevilla thanks to a well-struck volley from Aduriz in the centre of the penalty area after 13 minutes.
“It was a difficult game and we knew that we would have to take our chances as well as defend well,” Athletic full back Andoni Iraola told reporters.
“We were unable to get more goals but in the end it didn’t matter. Sevilla are a physical side, especially in midfield, and it was a hard fought game with a lot of fouls.”
Real moved top with a 4-0 win at Granada on Saturday and Valencia are now ahead of Atletico Madrid on goal difference while Barcelona are fourth, a point behind, after their 1-0 home defeat by Celta Vigo, their second loss in a row.
Sevilla are fifth, behind Barcelona on goal difference.
David Barral and Victor Casadesus were both on target as Levante moved off the bottom of the table with a 2-1 home win over Almeria, whose consolation came from Jonathan Zongo.
(Editing by Mark Meadows; [email protected]深圳桑拿网会所,; +44 20 7542 7933; Reuters Messaging:; mark.meadows.reuters深圳桑拿网会所,@reuters深圳桑拿网,)