Robbie Keane missed the best chance of the night on his Liverpool debut, just 24 hours after his £20million move to Anfield.
Keane played the first half of the friendly in Castellon, Spain, where his appearance was upstaged by the heroes' reception for the members of the Euro 2008 winners.
In the end Liverpool maintained their unbeaten record in pre-season matches, aware that their chances of adding Gareth Barry to their ranks seem to be dead.
Aston Villa's decision to end the negotiations over Barry earlier in the day was met with a strict 'no comment' from Liverpool but still dominated the pre-match discussions. Whether that is the end of the matter only time will tell.
The game was held up for several minutes as seven of Spain's victorious Euro 2008 side received ovations and presentations.
Four of those players were from Liverpool, Jose Reina, Alvaro Arbeloa, Xabi Alonso and Fernando Torres. Villarreal had Marcos Senna, Santi Cazorla and Joan Capdevila.
All seven were amusingly given small yellow submarine toys to mark the occasion, due to Villarreal's nickname.
Keane made his debut up front alongside another new boy, French teenager David Ngog, and both could have got their names on the scoresheet in the first period.
First, Keane was set up by fine work from Steven Gerrard - back following injury - and Yossi Benayoun. The new £20million man beat two players but lifted his shot over the bar.
Ngog, signed from Paris Saint Germain, saw a side-footed effort saved by Diego Lopez after Benayoun's pass.
Lopez had saved well from a Gerrard curler, but Villarreal had their moments.
The Spanish league runners-up forced Diego Cavalieri into good saves from Cani, ex-Arsenal man Robert Pires and Angel before Ariel Ibagaza hit a post with Joseba Llorente's follow-up deflected over by Stephen Darby.
Liverpool made nine changes at the break, including two teenagers on up front, the excellent Spanish youngster Daniel Pacheco and Hungarian striker Krisztian Nemeth, the reserves' top scorer last term.
Keane and Gerrard were among those taken off, leaving Benitez with a very youthful side including Jay Spearing and Emiliano Insua against Villarreal's experience.
Liverpool were under a lot more pressure in the second period, but Pacheco should have scored when put clear, only to drag his shot wide. Then Nemeth fired over from 20-yards.
With 20 minutes left Torres, Arbeloa and Alonso finally appeared - to a massive ovation from the home support.
Then with 10 minutes left, former Villarreal goalkeeper Reina came on for a cameo appearance, having rushed to the Madrigal stadium after being at the birth of his second child.
He too was given the hero treatment, the game now little more than an exhibition.
Benitez evaded questions over the Barry saga. Benitez, though, insisted on his 'party line' response to questions about Barry, saying, 'I would prefer to concentrate on the game and my squad'.
He added: 'I was really pleased with the situation on the pitch tonight. Robbie Keane did well, he had every chance to score but could not manage a goal.'
And when questioned again on the Barry subject, he said: 'I think we have quality in the squad and I would prefer to concentrate on the game.'
Benitez added: 'I feel the quality is improving, it is better than last season, and this match has been of benefit to the squad and for me to see several young players in action.'