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Diego Simeone's side had overturned an early deficit to beat Eibar three days earlier and were at it again at the Wanda Metropolitano, this time inspired by Joao Felix.
After a superb long-range Uros Racic opener stunned Atleti, their record signing scored his first LaLiga goal since November 7 to level matters and later laid on the second for Luis Suarez, Thursday's two-goal hero.
Substitute Angel Correa - on for Joao Felix - made sure of another win, which represented a vital response to Real Madrid's own triumph on Saturday, maintaining a healthy gap while the Rojiblancos still have a game in hand.
A lively, open start perhaps out of keeping with a typical Atletico match saw early chances at both ends, with Jaume Domenech denying Jose Gimenez and Jan Oblak blocking from Manu Vallejo before the spectacular 11th-minute breakthrough.
The Atleti goalkeeper was this time helpless at full stretch as Racic sensationally picked out the top-right corner with a swirling left-footed strike from 25 yards.
But the host was level midway through the first half when Joao Felix beat Thierry Correia to a deep corner and prodded beyond Domenech as Valencia's appeals for a foul somewhere in a busy penalty area fell on deaf ears.
And Valencia was fortunate not to concede a penalty shortly before half-time as Thomas Lemar stole in ahead of a dozing Maxi Gomez to reach a bouncing ball inside the box, only to see the foul given the other way.
Atleti continued to turn the screw and had their reward eight minutes after the restart, with Gabriel Paulista inexplicably standing off Suarez as he took Joao Felix's pass and calmly finished into the bottom-right corner from the left side of the area.
The result never seemed in serious jeopardy thereafter and Marcos Llorente cut a low ball back for Correa to sweep in 18 minutes from time to seal the points.
