Play had hardly started before Llorente was celebrating Valladolid's opening goal.Valladolid's Joseba Llorente was on target in the seventh second of the 2-1 home win over Espanyol, and was eventually credited with the second quickest strike in the Spanish top flight.
Llorente was given a time of 7.3 seconds.
Dario Silva of Malaga was timed at 7.2 seconds when he set the record - coincidentally against Valladolid - in December 2000.
Raul wasted little time in putting Real on their way to victory in the local derby with Atletico. Llorente added another after 33 minutes as Espanyol's hopes of climbing up to third place in the table were dashed.
Espanyol pulled a goal back through Marc Torrejon after 58 minutes but Valladolid held on for their fourth successive victory which pushed them up to seventh.
Espanyol stay in fifth place.
Raul had a simple task to sidefoot Real's early opener from two meters, after Robinho had created the opening from the left wing.
Atletico responded well, Thiego Motta heading against the bar, Iker Casillas having to save brilliantly from Raul Garcia and Kun Aguero's shot shaving the bar.
Unhappily for the hosts their efforts were unrewarded and four minutes before the interval Ruud van Nistelrooy put Real further ahead with his 12th goal of the season.
Casillas kept a clean sheet for the sixth consecutive game but there was one setback for Real, whose central defender Pepe went off with a calf strain after 15 minutes.
They already have defenders Gabriel Heinze and Christophe Metzelder out injured.
Atletico have not beaten Real at home since October 1999.
Ander Gaitano, who replaced the sacked Victor Fernandez as Real Zaragoza coach on Monday. started his reign with 3-1 defeat of Murcia. It was Zaragoza's first taste of victory in 10 league games.
Diego Milito scored twice for Zaragoza, taking his haul for the season to 13.
Athletic Bilbao had Francisco Yeste sent off in the 62nd minute of their 2-0 home loss to Osasuna. The visitors made their advantage pay when Cape Verde international Dady converted a 67th minute free-kick and laid on another for Carlos Vela two minutes later.
In the late match Thierry Henry's 31st minute gave Barcelona a 1-0 home win over Racing Santander.
The Frenchman was on hand to tap the spinning ball into the net from close range after Navas' slice ended up at his feet.
Barca looked unimpressive until Lionel Messi came on after 66 minutes for his first game in a month after recovering from a torn left thigh muscle.
The Argentine winger, who was second in the voting for the 2007 FIFA World Player of the Year last month, immediately added a bit of pace and bite to the Barca attack although they failed to add another goal.
The win keeps Barca within seven points of leaders Real.
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