Red Bull's Sebastian Vettel romped to his seventh pole position of 2011 at the European Grand Prix.
The world champion set a new record lap time around Valencia's street circuit for the second time on Saturday as he beat team-mate Mark Webber.
McLaren's Lewis Hamilton and Ferrari's Fernando Alonso aborted their final runs and will share the second row.
Jenson Button, who won the last race in Canada, starts sixth for McLaren with Mercedes' Michael Schumacher eighth.
There had been speculation before qualifying that a new directive from F1's governing body, the FIA, could rein in Red Bull's pace by as much as half a second.
The FIA had sent a note to the teams advising them that they will no longer be allowed to alter their engine maps - which is how the engine governs fuel usage - between qualifying and the race.
But just as Red Bull had predicted, the directive had no effect on this season's pecking order.
"Who's on top? Red Bull and Red Bull, so they are going to have to find something else I'm afraid," commented BBC F1 analyst Eddie Jordan.
"Hamilton can only drive what he's been given and, despite his problems in recent races, if he continues to drive well he will get his just rewards.
"We've been critical of Button but his qualifying is just not on par with his racing."
Vettel, who had been fastest in morning practice, set the benchmark in the final phase of qualifying and then decided to abandon a final run as his rivals again failed to overhaul him.
"It was a very good day for us," said the 23-year-old German, who now has 22 career pole positions under his belt.
"It's quite a tricky circuit and so to get every single corner right is quite tough but my first run was quite good. It's a good point to start tomorrow."
Vettel took pole here last season and went on to complete a straightforward race victory.
Webber has had a low-key weekend but hit form at the right time, snatching second from Hamilton as he finished just 0.188 seconds behind Vettel.
McLaren ran with updated front and rear wings in Valencia but it was the tyres which caught them out as the street circuit warmed up under 26C temperatures.
"I wasn't expecting to be so high up after final practice [because we were struggling] to switch the tyres on," said Hamilton.
"It's a fantastic job by the guys, I tried to improve on the last lap but I just bailed out and hopefully have saved the tyres for the race."
McLaren will still go into Sunday's race in confident mood as their pace over a race distance is strong but Button was left ruing that he was not able to put himself in a better starting position.
"It's not very good," he said. "I just didn't expect it today.
"In Q3 I had massive oversteer and couldn't get any rear grip. It's so frustrating. Maybe in the heat our balance isn't working. I'm sure we can change the balance for the race."
Despite seeing Red Bull lock out the front row, McLaren team principal Martin Whitmarsh is confident his drivers will have better pace in the race.
"Let's see what's possible in the race," said Whitmarsh. "It's our business to believe we can beat the Red Bulls. In the last few races we've had a quicker race car and you can overtake this season as has been shown.
"It will be tough, but it's easy to get strategy wrong - they could get it wrong, we could get it wrong. We'll see."
Alonso, who made two mistakes on his final run before aborting the lap, believes he achieved the maximum he could in front of his home fans.
"I feel happy. it's been the best qualifying of the year apart from Canada," said the Spaniard. "This is our maximum position at the moment as Red Bull are out of reach.
"We have one McLaren in front and one behind so we're about the same. Hopefully we can do something tomorrow and I think a podium is the realistic target.
"In qualifying we see the real pace of all the cars and the Red Bull is the clear favourite, so we'll look at third. We will need to overtake just one car for that.
"I'm sure Lewis [Hamilton] will be aggressive on the first corner and if there are any accidents, I will be ready."
The second phase of qualifying was interrupted when Pastor Maldonado's Williams juddered to a halt in the middle of the track at Turn 20.
The Venezuelan, who is determined to chase his first points this weekend, will line up in 15th, with team-mate Rubens Barrichello two places ahead.
Paul di Resta has had a difficult first experience of Valencia after Force India reserve Nico Hulkenberg damaged the Scot's car in first practice on Friday, which limited Di Resta's running on Friday afternoon.
"It was difficult and after Friday I was always going to be on the back foot," said Di Resta, who starts in 12th.
"You have to stay positive and we're in a position where we can fight for points. The only concern is that we haven't done a long run on high fuel."
For the third race in a row, Toro Rosso's Jaime Alguersuari failed to make it through the first stage of qualifying.
The Spaniard has again fended off speculation in Valencia that Australian reserve Daniel Ricciardo is poised to take his seat.
Alguersuari, who took his first points of the season last time out in Canada, insisted his place in the team was not under pressure but conceded he was "not 100% happy with everything going on."
He added: "I don't think about my future and I just see myself with this team and with this [Red Bull] family. I can bring much more to the team this year and next year in F1."