The Australian had beaten Lewis Hamilton’s time halfway through the hour, but while Vettel made big gains on soft tires at the end, Webber's earlier benchmark remained his best time. He improved in individual sectors, but did not manage to put a full lap together.
McLaren ended up third and fourth with Hamilton and Jenson Button, as Michael Schumacher continued his promising form in Spain by taking fifth for Mercedes.
The Ferraris of Felipe Massa and Fernando Alonso were back in sixth and eighth, with Mercedes' Nico Rosberg in between. The German was beaten by his team-mate in all the three practice sessions.
Adrian Sutil managed to post the 10th best time, behind Robert Kubica (Renault), despite stopping his car at the side of the track with five minutes to go because his Force India car suddenly lost power.
There was one red flag stoppage 20 minutes in, when Sauber's Kamui Kobayashi and Renault's Vitaly Petrov had separate incidents at Turn 4. While the Sauber spun harmlessly into the gravel, the Renault snapped violently left as it braked and crashed into the tire wall, damaging both ends.
Lotus was the best of the new teams, with Jarno Trulli slightly ahead of Heikki Kovalainen, and both just over 4s off the leader’s pace. Hispania's Bruno Senna was last, having been stranded in the garage with a leak on his car for much of the hour.
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