Australian Mark Webber took pole position for the Spanish Grand Prix on Saturday and ended Red Bull teammate Sebastian Vettel's bid for a sixth in succession.
Formula One world champion Vettel, winner of three of the first four races of the season from pole position as well as last year's final round in Abu Dhabi, will start alongside on the front row.
McLaren's Lewis Hamilton and Ferrari's Fernando Alonso, favourite of his home Spanish crowd, will line up together on the second row on Sunday.
"I don't think we can speak of big disappointment, we made a good step forward," said Vettel, who will still be making his 10th successive front row start.
"He (Webber) did a better job today."
The Australian has yet to win a race this season but was triumphant last year from pole position at a circuit where the winner has started in the top slot for all of the past decade.
However, the new moveable rear wing (DRS), kinetic energy recovery system and quick-wearing Pirelli tyres should make Sunday's race far less predictable with plenty of overtaking and pitstops expected.
"I'll have a good sleep tonight, come back and do the best job I can tomorrow," Webber said after his first pole since Belgium last August and seventh of his career.
He had been fastest throughout practice on Friday and, with drivers eager to save their soft tyres for the race knowing that the harder tyres carried with them a big drop off in performance, wrapped up pole with his one flying lap in the final qualifying session.
The Australian was parked up in the garage and out of the car with more than a minute of the session remaining, with McLaren recognising the futility of making any attempt to wrest pole from him.
Michael Schumacher, the seven-times world champion who won six times in Barcelona with Benetton and Ferrari before making his comeback with Mercedes, did not set a timed lap in the last part and will start 10th.
That was one place behind Venezuelan rookie Pastor Maldonado, making his first appearance in the top 10 with Williams.
Further back, Team Lotus celebrated Heikki Kovalainen's 15th place on the grid, their best qualifying performance in dry conditions.
Renault's Nick Heidfeld did not take part in qualifying after his car caught fire in final practice and could not be rebuilt in time.
Fears that the Hispania and Virgin cars would not make the qualifying standard, based on times in practice, proved unfounded.