Atletico Madrid overcame the heroics of Valencia goalkeeper Diego Alves to win 2-0 at the Mestalla.
The Brazilian saved two penalties, but second-half strikes from Antoine Griezmann and Kevin Gameiro settled matters.
The result keeps Diego Simeone's side in early-season contention for LaLiga glory.
However Valencia, who replaced Pako Ayestaran with Cesare Prandelli as head coach this week, continue to struggle near the bottom.
Ayestaran replaced Gary Neville at the helm in the spring but could not prevent a bottom-half finish in LaLiga and made a dire start this term. Valencia were bottom of the table when Ayestaran was dispensed with on September 20.
Former Italy boss Prandelli has his work cut out and this defeat, Valancia's fifth in seven league games, showed that clearly despite the quality of the opposition.
Among many other stops, penalty specialist Alves denied Griezmann from the spot in the 44th minute and likewise Gabi in the 69th minute, the latter soon after the visitors had taken the lead.
With chances coming at both ends, Valencia gamely fought to get level, but they were caught on the counter-attack by Gameiro in stoppage time.
Atletico's Saul Niguez had the first effort on goal but Alves was equal to the close-range effort.
Alves was twice called into action by long-range shots midway through the opening half, first by Griezmann who fired at the top-left corner and soon after when Koke aimed at the bottom-left corner.
Valencia finally had an effort on goal in the 37th minute, Jan Oblak comfortably saving from Jose Gaya.
Saul and Martin Montoya required treatment shortly before former Manchester United winger Nani conceded a penalty for a foul on Angel Correa, but Griezmann - who missed from the spot against Bayern Munich in midweek - saw his spot-kick saved by Alves.
Before the break Nani somewhat redeemed himself by setting up Rodrigo who forced a low save by Oblak.
Atletico continued to press in the second period, Filipe Luis soon forcing Alves into a save.
Tempers flared as Griezmann and Manchester City loanee Eliaquim Mangala were booked for bad challenges around the hour mark.
Shortly after, Alves kept Fernando Torres out, saving low to his right, but moments later Griezmann broke the deadlock when he emphatically finished left-footed into the top-right corner.
Alves was again forced into action, this time denying Gameiro.
The in-form keeper then excelled himself further. After Mario Suarez fouled Griezmann, Alves went to his right to save from Gabi.
Nani had two shots on target and team-mate Daniel Parejo also drew a save from Oblak as Valencia pressed for an equaliser.
Gabi almost doubled the lead when he hit the right post with a drive from outside the box.
Atletico's Torres and Valencia duo Mangala and Santi Mina went close with headers in the closing moments.
But with the hosts pressing for a leveller, Atletico broke and Gameiro made the result certain with a left-footed finish from close range after dribbling into the box virtually unchallenged.