Benitez led Valencia to the Spanish league title in 2002 and 2004 before leaving for Liverpool and is the only coach to have denied Real Madrid and Barca the top spot in the last 11 years.
Unai Emery is now at Valencia's helm and, although they finished third in the last two years, they have been a long way off the pace after being forced to sell many of their top players to help pay off the club's debts.
They have started the new campaign at a gallop, however, and sit atop the standings on goal difference from promoted Real Betis with a perfect nine points after a 1-0 win at Sporting Gijon on Saturday.
"We need to remain calm, the league has only just started," Emery said in Gijon. "We can enjoy it but there is still a long way to go."
Barca lie third with seven points after suffering a rare slip up when they drew 2-2 at Real Sociedad a week ago, but they quickly put that right with an 8-0 pummeling of Osasuna on Saturday.
World Player of the Year Lionel Messi scored a hat-trick and tops the scoring charts with five goals, where he is joined by Valencia striker Roberto Soldado.
Soldado, 26, stepped in to fill the void after Spanish international David Villa was sold to Barca last year, and is considered a potential partner for Villa at Euro 2012.
NEED TO ADAPT
Real's shock 1-0 defeat at Levante on Sunday meant they slipped to fifth with six points. They are on the road again at Racing Santander on Wednesday.
Real had midfielder Sami Khedira sent off in the first half at Levante in a niggly, bad-tempered battle, and coach Jose Mourinho expressed his concern afterwards that his players needed to adapt to those tense situations at smaller grounds.
"There are players here who are very good playing on the great stages but who arrive here and are incapable of adapting to the situation," Mourinho complained.
The Portuguese will hope to have his compatriot Cristiano Ronaldo back to full fitness. The forward was used as a substitute only against Levante as he recovered from an ankle injury.
Marcelo Bielsa is seeking his first league win at Athletic Bilbao when they visit big-spenders Malaga on Wednesday.
The former Argentina and Chile boss is under pressure as he tries to change a club famed for its pacy, aggressive football, as embodied by leading figures Javi Martinez and Fernando Llorente, into a side with a patient, possession-based style.
When asked if he had a message for fans after Sunday's 3-2 defeat at home to Real Betis, he said: "We have the points we have [one] and the style of play is what we have seen so far.
"They need to be patient... anything more would be words that don't mean anything."
