(CNN) -- Real Madrid have closed the gap on Spanish league leaders Barcelona after the defending champions dropped their first points of the season on Saturday night.
Raul, left, celebrates his first goal against Valladolid with Raul teammate Esteban Granero.
The European champions were left just one point ahead of their fierce rivals following a frustrating 0-0 draw away to fifth-placed Valencia which ended their bid to establish a club record of seven wins at the start of a season.
Real earlier returned to winning ways with a 4-2 victory at home to Valladolid, with captain Raul celebrating his new club appearance record with the opening two goals.
The 32-year-old was presented with a commemorative trophy by club president Florentino Perez before the game for breaking the mark of 710 outings in the white shirt set by Manolo Sanchis.
The striker added to his all-time Real scoring tally as he netted twice in five minutes to help Real bounce back from the 2-1 defeat by Sevilla before the international break.
First he diverted a low cross from midfielder Esteban Granero into the net in the 13th minute, then made it 2-0 as Marcelo delivered from the opposite left flank soon after.
Struggling Valladolid have twice shipped seven goals at Real in the past decade, but this time showed more fight to pull a goal back in the 28th minute from winger Nauzet Aleman's 25-yard free-kick.
Brazil fullback Marcelo matched that stunning strike to restore Real's two-goal buffer on the stroke of halftime as he was given space to unleash a thunderbolt from similar distance.
Valladolid hit back again eight minutes after the interval as Diego Costa set up Marquitos, who fired a first-time shot past Iker Casillas -- who then did well to deny Nivaldo an equalizer.
However, substitute Gonzalo Higuain stretched the lead again in the 79th minute after being put free by Xabi Alonso, chipping the ball over Jacobo Sanz to give Real a morale-boosting win ahead of Wednesday's Champions League clash at home to AC Milan.
Barcelona will also have home advantage as they continue their European title defense at home to Rubin Kazan on Tuesday, and will hope for a better showing than they managed at the Mestalla.
Valencia will be left ruing missed chances, with Juan Mata particularly guilty.
Barca keeper Victor Valdes did well to tip over an ambitious effort from halfway by Pablo Hernandez, and also denied Spain striker David Silva from point-blank range.
Rodriguez Pedrito went closest for the visitors, who left summer signing Zlatan Ibrahimovic on the bench, when his shot on the turn was deflected wide by David Navarro with keeper Cesar Sanchez caught out of position.
Cesar almost gifted Yaya Toure a late winner, but scrambled to recover the ball before it could cross the line.