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Manuel Pellegrini's Real Betis became the first side to score against Villarreal in LaLiga this season, and secured three points at the Estadio Benito Villamarin.
Villarreal had a golden chance to take the lead in the first half, when Martin Jackson found Gerard Moreno, but the Spain international's effort was fired directly at Betis goalkeeper Rui Silva.
Betis defended solidly throughout the game, with centre-back Luiz Felipe repeatedly foiling the visitors' attempts to get through on goal.
Receiving the ball on the right side of midfield, Betis' £8million summer-signing Luiz Enrique whipped a scintillating ball towards the back post that was met by Rodri to put the home side ahead.
The result sees Betis move up to third in the LaLiga table, just three points behind league leaders Real Madrid.
Pellegrini's side will aim to maintain their positive momentum in their next league fixture when they play host to LaLiga new boys Girona.
Meanwhile, Emery's Villarreal will look to rebound against strugglers Sevilla at the Estadio de la Ceramica on Sunday.
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