Sebastian Vettel topped the times for Red Bull on Friday after clocking the fastest lap during the second practice session ahead of Sunday's European Grand Prix.
The 24-year-old, second fastest in the morning session, made the most of the warmer weather conditions and clocked a fastest lap time of 1min 39.334sec, edging out fellow German Nico Hulkenberg of Force India by one tenth of a second.
As in the overcast morning session, drivers continued to lock up their brakes early on as teams struggled to find the right brake balance to deal with the demands of the Valencia street circuit.
As the sun began to shine and the track temperature continued to rise midway through the session, Ferrari driver Spaniard Fernando Alonso went fastest before his fellow countryman Pedro de la Rosa of Hispania held up proceedings by crashing into the barrier at turn 14.
As soon as the track was clear, defending drivers' champion Vettel, who has won both the previous races in Valencia, clocked his fastest time approaching the hour mark.
Despite a flurry of efforts from other drivers, Hulkenberg came closest to matching the German's time before drivers changed setup and began testing under heavier fuel loads.
Japanese Kamui Kobayashi of Sauber wound up third fastest ahead of Mercedes driver German Michael Schumacher and Brazilian Bruno Senna of Williams.
Briton Paul di Resta was sixth fastest in the other Force India car followed by double champion Alonso for Ferrari and Frenchman Romain Grosjean of Lotus.
Australian Mark Webber wound up ninth fastest despite finishing just half a second slower than team-mate Vettel.
German Nico Rosberg was tenth quickest in the second Mercedes.
Both McLaren drivers and compatriots Jenson Button and Lewis Hamilton could not find the pace to match the frontrunners and finished the session 12th and 14th respectively.
Felipe Massa also appeared to struggle and wound up 15th fastest.