With Barca and Villarreal tied at 1-1 after first-half goals from strikers David Villa and Nilmar, Argentina forward Messi showed why he is the reigning World Player of the Year with a finish of breathtaking skill in the 58th minute at the Nou Camp.
Twice exchanging passes with Pedro, he sped past the static defenders and, as Diego Lopez sprinted out, lifted a delicate angled chip over the Villarreal goalkeeper with his weaker right foot and into the empty net.
The Barca faithful roared their approval and chants of "Messi, Messi, Messi" rang out around the giant arena.
His second in the 83rd was less spectacular but made the game safe against a dangerous Villarreal side.
Pedro's shot ricocheted into Messi's path and he deflected the ball past Lopez low into the corner.
They were the 23-year-old's ninth and 10th league goals of the campaign, leaving him one short of Real Madrid forward and top marksman Cristiano Ronaldo.
"We are very happy with the win because we were facing an important rival who play very well," Barca fullback Daniel Alves told reporters.
"(When) we are playing at our level it's difficult to beat us here at the Nou Camp," he added.
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