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The 22-year-old, whose team have taken pole position in all four races so far this season, lapped the Circuit de Catalunya in one minute 20.528 seconds with Australian team mate Mark Webber 0.704 slower.
Germany's Sebastian Vettel limbered up for Spanish Grand Prix qualifying on Saturday by leading a Red Bull one-two at the top of the timesheets in final practice.
The 22-year-old, whose team have taken pole position in all four races so far this season, lapped the Circuit de Catalunya in one minute 20.528 seconds with Australian team mate Mark Webber 0.704 slower.
McLaren's world champions Lewis Hamilton and Jenson Button, the overall championship leader, were third and fourth with Michael Schumacher fifth and again back on the pace in a Mercedes changed to his liking.
The seven times world champion, returning at the age of 41 after three seasons out, was eclipsed by team mate Nico Rosberg in the first four races but has been quicker than him in every practice session in Barcelona.
Rosberg was seventh with Fernando Alonso, making his home debut as a Ferrari driver, eighth on a sunny morning at the circuit north of Barcelona. The Spaniard's Brazilian team mate Felipe Massa was sixth.
The session was halted briefly after 20 minutes when Renault's Russian rookie Vitaly Petrov crashed heavily into the tyre wall after losing control on a kerb made slippery by overnight rain.
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