Despite a makeshift defense and coming off a European Super Cup victory just three days before, Barcelona responded to Real Madrid's 6-0 rout of Zaragoza over the weekend with another display of its own beautiful game.
Thiago and Cesc Fabregas struck before halftime, Alexis Sanchez extended the lead and Messi capped the victory at Camp Nou stadium with a pair of late goals.
Barcelona has now gone undefeated in all competitions at home since last season's home opener.
"We are very happy considering where we came from," said coach Pep Guardiola, who has already added two pieces of silverware to Barcelona's trophy case this summer. "This team has demonstrated that it always wants more. The win of the Spanish Supercup gave us an extra push to win more."
With starters Carles Puyol, Gerard Pique, Adriano and Maxwell all out with injury, and Dani Alves serving a suspension from last season, Guardiola experimented with a three-man defensive line with Eric Abidal alongside reconverted midfielders Javier Mascherano and Sergio Busquets.
Even with the new system and Spanish internationals Xavi Hernandez and David Villa on the bench, Guardiola's team continued to mesmerize with its possession-based attack.
Thiago broke through in the 25th when the 20-year-old Spain midfielder received the ball outside the area and coolly slid forward before picking his spot and slotting the ball through a pack of defenders into the right side of the net.
Reminiscent of Barcelona's second goal in the European Super Cup on Friday, Messi and Fabregas continued to show the connection they developed as teenage teammates as the Argentine star left Fabregas with only goalkeeper Diego Lopez to round and tap home on the halftime whistle.
While Barcelona was content to strangle Villarreal's passing game with its control of the ball in the first half, it quickly put the game out of question right out of the break.
Sanchez netted his first goal in an official game for his new team in the 47th when he latched on to a lobbed pass from Thiago and fired past Lopez into the far side of net.
Four minutes later Andres Iniesta played Messi through the center of the defense for him to beat Lopez one-on-one.
The demoralized Villarreal defense collapsed completely in the 74th when another one-touch combination left Thiago alone on the flank to cross for Messi to deflect in his sixth goal in four games.
For Guardiola, his team's success goes through its midfield.
"It is true that Messi and Cesc look for one another, but Iniesta did so as well. Thiago participated, and Seydou (Keita)," he said.
"On this team it is inconceivable that if one player makes a run, his teammate doesn't pass him the ball."
Over the weekend, Cristiano Ronaldo scored a hat trick to lead Real Madrid to its thrashing of Zaragoza.
Also, it was: Valencia 4, Racing Santander 3; Sporting Gijon 1, Real Sociedad 2; Granada 0, Real Betis 1; Atletico Madrid 0, Osasuna 0; Athletic Bilbao 1, Rayo Vallecano 1; Getafe 1, Levante 1; Mallorca 1, Espanyol 0; and Sevilla 2, Malaga 1.