Nine-man Sporting Gijon claimed a remarkable late 1-1 draw with Villarreal thanks to an injury-time penalty from Diego Castro.
Villarreal looked set to put their poor recent domestic form behind them as they took a 29th-minute lead through free-scoring striker Giuseppe Rossi before then seeing Sporting lose defenders Jose Angel (65 minutes) and Rafael Sastre (90) to red cards.
However, there was a late twist in the tale as struggling Sporting claimed a dramatic last-gasp equaliser from Castro, who showed remarkable composure and self-assurance in the circumstances to chip his penalty down the centre of the goal.
The result means Villarreal missed the chance to move to within one point of third-placed Valencia at the top of the standings, and leaves the Yellow Submarine with just one win from their last seven league games. For 17th-placed Sporting, the draw leaves them three points above of the relegation zone.
Villarreal came into the match with confidence boosted by their impressive 3-2 win over Bayer Leverkusen in the first leg of their UEFA Europa League last-16 tie on Thursday, and they looked on course to complete a successful few days thanks to Rossi's first-half strike.
Sporting goalkeeper Ivan Cuellar failed to collect Borja Valero's corner and Rossi took advantage by tapping into an empty net at the far post for his fifth goal in his last six games. It was also the Italy international's 15th league goal of the season and 25th in all competitions.
It also looked like being a match-winner, especially when Sporting were reduced to ten men with 25 minutes to go when Jose Angel was shown a second yellow card. He was cautioned seemingly for something he said to the referee while Cuellar was being treated for an injury that eventually forced the visiting goalkeeper out of the match.
Jose Angel appeared stunned by the decision but to their credit Sporting overcame that setback, plus the loss of Cuellar, and pushed hard for an equaliser despite their numerical disadvantage.
They seemed to have been rewarded for their efforts when David Barral got in behind the home defence in the 78th minute and fired a rising shot past Diego Lopez, but the ball came back off the near post.
Sporting's hopes of fashioning another chance as good as that looked unlikely, especially when they lost Sastre to a straight red card after he hauled down Rossi as the former Manchester United man attempted to latch onto a ball over the top.
However, two minutes after that incident Sporting were given an ideal chance to salvage a point when Nacho Novo was sent tumbling in the box by Gonzalo Rodriguez, and Castro did the rest with an ice-cool penalty past the diving Lopez.