After scoring a hat-trick against Celtic in midweek, the Barcelona frontman scored either side of the break to take his tally to 10 goals, alongside his 10 assists for the season.
And Gerard Martino’s side extend their lead at the top of the Spanish top-flight to three points prior to Atletico’s clash with Valencia tomorrow night.
Without Lionel Messi – still in Argentina for rehabilitation – Daniel Alves, Adriano and Carles Puyol to name a few, Barca’s performance lacked the usual co-ordination and cohesion expected of the Spanish champions.
But after six minutes, an otherwise stingy Villarreal rearguard handed Alex Song a super opportunity to score, as he chested a corner-kick from Neymar, before rifling a right-foot shot against the post.
Former La Masia graduate Giovani Dos Santos was a lonely figure at the summit of Villarreal’s attack, in which he was flanked by Javier Aquino and Hernan Perez on the counter-attack.
There were fleeting glimpses of the raw pace in Marcelino’s team, but Barcelona were always in control without really flashing their known talents.
Indeed, “Tata” Martino’s men needed a soft spot-kick decision from the match referee to beat Sergio Asenjo after 30 minutes.
Neymar’s fairly aimless cushioned pass struck Villarreal right-back Mario Perez’s arm and the Brazilian made no mistake, dispatching the penalty to become FCB’s fifth spot-kick scorer of the campaign.
Barcelona’s next chance came six minutes from the break, as Asenjo blocked impressively from Alexis Sanchez who looked to pass the ball into the bottom corner.
However, it was the team in yellow that returned from the interval with an extra edge on their opponents and they were back level within 120 seconds of the restart.
Captain Mateo Masucchio found a yard to beat Marc Bartra in the six-yard-box, from Trigueros’ corner-kick, before powerfully bashing the ball home to level the scores.
Marcelino’s side were more expansive and keener to support Dos Santos in attack and the Mexican came close a minute later to scoring against his former employers, cutting infield and driving past the post.
But the introduction of Xavi Hernandez seemed to alter the balance in Barca’s favour with the ineffective Song making way. They eventually found the breakthrough on the 68th minute with Neymar tucking home his second of the evening.
Cesc Fabregas, who had been anonymous for the majority of the match, picked out Sanchez with a neat diagonal at the far-post and the Chilean laid off to Neymar who found the net from a few yards out.
The 21-year-old becomes the first Brazilian to score at least six goals in a season for Barcelona since Ronaldinho’s total of eight in 2007/08.
Villarreal struggled to recover and looked jaded in the closing stages of the match, but they could rely on the excellent talents of on-loan Atletico Madrid keeper Asenjo for good measure.
The 24-year-old pulled off a fine stop to deny Andres Iniesta who smashed a sweetly-struck volley towards the bottom corner of the goal after 81 minutes.
But despite facing stiff criticism following their defeat in Bilbao, Martino picked up another three points – and Neymar continued his fantastic vein of form.
In Saturday's late game, a Roque Santa Cruz header gave Bernd Schuster's misfiring Malaga side a 1-0 win over visiting Getafe to put them five points above the relegation zone.
Mid-table Granada won 2-0 at lowly Rayo Vallecano with goals in either half from Fran Rico and Riki.