The team known as "the Yellow Submarine", because of their canary-coloured strip, won promotion back from the second division, along with Elche and Almeria, after a year in the wilderness following a dramatic fall from grace.
The European football regulars were relegated on the final day of the 2011-12 campaign, having started the season in the Champions League.
However, they have bounced back at the first attempt and are the favourites among the newcomers to re-establish themselves among the big boys due to their experience and financial solidity.
They are only team to have broken the La Liga duopoly of Real Madrid and Barcelona in the last nine years, when they finished second behind Real in 2008 and ahead of Frank Rijkaard's Barca.
They lack the history and honours of relegated clubs Real Zaragoza, Deportivo La Coruna and Real Mallorca, who have all recently had to go into administration to resolve their financial problems, but go up boasting a budget of 50 million euros ($66.18 million).
Villarreal quickly rid themselves of their highest earners following relegation, but have made a statement of intent on their return risking a reported 10 million euros ($13.24 million)on Mexico forward Dos Santos, signed from Real Mallorca.
The gifted 24-year-old, who already has over 60 international caps, came up through the Barca youth system but since leaving the Nou Camp in 2008 has wandered from Tottenham Hotspur, to Ipswich Town, to Galatasaray, to Racing Santander and Mallorca.
He almost signed for Villarreal a year ago, the deal falling though when the club were relegated, and has worked before for current coach Marcelino, while at Racing.
In major shareholder and president Fernando Roig, owner of a tile manufacturing company, Villarreal have a relatively wealthy patron with his feet firmly on the ground.
He has said the club is debt free, a rarity in the cash-strapped world of La Liga.
Roig has taken the middle-distance approach to building a club with steady investment in facilities and players rather than the more typical "cash-dash" which has left so many Spanish teams teetering on the brink of extinction.
New Manchester City boss Manuel Pellegrini, who led Villarreal to the Champions League semi-final in 2006, has praised the way the east-coast club is run.
"The ideal model to run an institution is Villarreal. They are an example in every aspect," the Chilean said in a recent interview in El Pais.
"Villarreal work in a structured manner. They went down to the second division, but they have developed structures and they have a good administrative and footballing base."
One of the players Villarreal sold to help balance the books last year was Italy striker Giuseppe Rossi, the club's all-time top scorer, who returned with his new side Fiorentina for a pre-season friendly at the Madrigal last week, which the Italians lost 2-0.
"They have made some good signings and with the important players they already had from last season they have built a great team," Rossi told sports daily Marca.
"I predict a good season for them this year."
Tiny Alicante-based Elche led the second division from beginning to end last season and return to the top flight after a 24-year absence with survival as their number one objective.
It will be a similar story for Almeria, who won promotion through the play-offs, and return after two years in the second division.
The Andalucian side are managed by the youngest coach in La Liga, the 35-year-old Francisco Rodriguez, who was promoted from coaching the reserves in June after Javi Gracia failed to agree a contract extension. ($1 = 0.7555 euros)