And the world-record signing needed just two minutes of playing time to achieve it.
Ronaldo turned his man brilliantly in his own half and raced towards goal, skipping past two more defenders before drilling the ball past the six foot six inch frame of Diego Lopez into the bottom left-hand corner from 25 yards.
The goal followed up his feat of scoring just 49 seconds into last SundayÃ¢â‚¬â„¢s match against Xerez.
Travelling away to Madrid coach Manuel PellegriniÃ¢â‚¬â„¢s former side was to be the first real challenge for this new era of galacticos and, following RonaldoÃ¢â‚¬â„¢s sensational solo effort, they oozed confidence.
Their one-touch approach play was delightful and the blossoming understanding between Ronaldo and Kaka is one to rival that of Xavi and Messi at Barcelona.
Real had a chance to double their advantage on 23 minutes.
Kaka slid a through ball into Marcelo at the by-line and his pull-back found Argentine starlet Higuain who blazed a glorious chance over at close range.
As the game surpassed the half-hour mark, Villarreal were reduced to 10 men.
Club captain Gonzalo received his second caution for cynically preventing KakaÃ¢â‚¬â„¢s surge forward with a high boot into the BrazilianÃ¢â‚¬â„¢s chest.
Despite the reduction, the home side fought hard and the half was proving a tightly-contested affair as Real, as in their last fixture, failed to add to their early lead.
Ronaldo was set free in behind down the channels on several occasions, but delivered a poor final ball far too often.
He had the chance to net his brace shortly before half-time, but struck his left-foot volley high over the bar as he stood unmarked from a corner.
Villarreal began brighter in the second half and almost drew level on 47 minutes.
GutiÃ¢â‚¬â„¢s sloppy pass was latched onto by young Italian hotshot Giuseppe Rossi who drove towards goal before hitting a low shot that Casillas could only parry.
The biggest cheer of the evening came shortly after, as Guti, notoriously disliked away from the Bernabeu, was booked for petulantly kicking the ball away on the award of a Villarreal free-kick.
On 55 minutes, Higuain saw an effort terrifically cleared on the line by Angel Ã¢â‚¬â€œ who was proving far from what his name suggests as he tussled with Ronaldo throughout proceedings.
The game began to open up as the 10 men of Villarreal searched for an equalizer.
Cazorla had the home fans on their feet as his venomous strike veered just wide of goal from all of 30 yards.
Ronaldo was not to be the only record-breaker of the evening. The largely ineffective Higuain was replaced after the hour by Raul, who came on for his 524th La Liga appearance Ã¢â‚¬â€œ surpassing the milestone of 523 set by Manuel Sanchis.
Shortly after, Real finally made their man advantage count by notching a second goal.
Marcelo Ã¢â‚¬â€œ who was proving a danger on the left Ã¢â‚¬â€œ saw his attempted pull-back inside the box strike the arm of Angel and a penalty awarded.
Kaka took responsibility and sent Lopez the wrong way to score his long-awaited first in the famous white of Real.
Ronaldo came close to bagging a third for Real on 75 minutes with a trademark dipping free-kick that had to be pushed around the post by Lopez.
The home side settled for damage limitation as PellegriniÃ¢â‚¬â„¢s replacement at Villarreal, Ernesto Valverde, made several defensive substitutions.
RonaldoÃ¢â‚¬â„¢s ongoing feud with Angel resulted in confrontation in the closing stages. It was hard to blame Angel as the Portuguese superstar teased the right-back with a host of flicks and tricks throughout the 90 minutes.
Real and Barca already appear to be running away with this league, despite only leading third-placed Sevilla by three points, and are attracting large sums of money backing the pair to reign victorious until the first Ã¢â‚¬ËœEl ClasicoÃ¢â‚¬â„¢ meeting in round 12.
An ambitious punt, but not altogether unforeseen.
Villarreal: Diego Lopez, Angel, Gonzalo, Godin, Capdevilla, Cazorla (Pereira, 76), Eguren, Bruno, Cani (Marcano, 76), Rossi (Pires, 65), Nilmar
Real Madrid: Casillas, Lass, Sergio Ramos, Albiol, Marcelo, Granero, Gago, Guti (Diarra, 81), Kaka (Van der Vaart, 75), Higuain (Raul, 65), Ronaldo
Man of the Match: Cristiano Ronaldo Ã¢â‚¬â€œ Sensational early strike changed the complexion of the game and the winger proved a threat all evening.
WednesdayÃ¢â‚¬â„¢s other La Liga results:
Atletico Madrid 2-2 Almeria
Espanyol 2-1 Malaga
Getafe 3-1 Valencia
Tenerife 1-0 Athletic Bilbao
Valladolid 1-2 Osasuna
Xerez 0-3 Deportivo
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