Robbie Keane and David Ngog made their debuts up front and both settled into the side quicky. Keane was linking up well with his new team mates and it was the £19m signing who had Liverpool's first real chance of the half.
Yossi Benayoun played a smart through ball to Keane on 27 minutes but unfortunately the ball got caught under his feet and when he digged it out he lifted his shot over the bar.
Benayoun also created a fine chance for Ngog just before the interval, again slipping through an excellent through ball but unfortunately the French striker's shot was saved.
Liverpool were coming under a lot of pressure at the other end with Diego Cavalieri having his busiest night yet in the Reds goal. He was forced to make a couple of saves, saw himself lobbed only for the goal to be correctly rued out for offside and saw a shot cannon back of his post. The rebound from that fell to Cani eight yards out who had the simplest of tap ins but Stephen Darby bravely flung himself in front of the ball to deflect the shot over the bar.
Rafa Benitez made nine changes at half time with only Cavalieri and Plessis remaining on the field. The changes made no difference to Villarreal who continued to put Liverpool under pressure. Cavalieri was again called into action to make a few saves before the Reds began to apply pressure of their own down the other end of the pitch.
Daniel Pacheco had the best chance of the half when he was played in behind the Villarreal defence. Unfortunately he took to many touches, allowed the defenders to get back and then opened up his body too much and sent his shot wide of the post.
Nemeth saw a couple of chances go over the bar before he was replaced by Fernando Torres on 70 minutes. Torres volleyed wide one clear chance and almost set up a header for Pacheco.
Jay Spearing almost won it for the Reds in injury time. Xabi Alonso sent over a deep corner which Spearing volleyed first time from 25 yards out. His shot went inches wide of the post. That was to be the final kick of the match.