Chukwueze, who was among the substitutes, was introduced in the 62nd minute of the game for Yeremi Pino and had a positive impact.
The winger who recently returned from a long injury layoff has now featured in four games for the Yellow Submarine but has yet to start a game.
Aissa Mandi put Villarreal 1-0 ahead in the 32nd minute before Gerard Moreno made it 2-0 in the 36th minute.
The win saw Villarreal climb to 13th place on 19 points in the league table while Rayo Vallecano sit 6th on 27 points.
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