Goals from Cani and Rossi have seen Villarreal defeat Atletico Madrid 2-0.
Cani came into the match for the suspended Borja, and quickly found himself on the scoreboard after nine minutes. Nilmar's through-pass was perfectly weighted for the midfielder to latch onto and poke it past David De Gea.
Villarreal looked the more promising to score again, as Giuseppe Rossi was dangerous in and around the penalty area, getting on the end of several passes, but was unable to get his attempt on goal to count.
Aguero made a surging run forward on the half-hour mark, giving his side some confidence, but some last-minute defending by Carlos Marchena meant the Argentine was stopped in his tracks.
Diego Lopez brought down Aguero on the verge of half-time in the box, but the referee blew his whistle for half-time, instead of a spot-kick. Several Atleti players surrounded the referee wanting more information, but were waived away.
The Yellow Submarines did not take long after the restart to find the back of the net again, as Rossi made it 2-0 on 52 minutes. Cani played a ball into the middle for the Italian, who twisted and turned his way to fire home past De Gea.
Nilmar had a chance to seal the match on the hour mark with a shot from outside the area but could only manage to hit De Gea in the legs.
Villarreal move into second place ahead of Barcelona on goal difference, making this their best ever start to the season.