Lewis Hamilton made it four pole positions in five races this season as he again left Mercedes team-mate Nico Rosberg trailing.
With Mercedes again proving to be way ahead of their rivals, Hamilton finished 0.168 seconds ahead of Rosberg as the all-conquering force in Formula One again locked out the front row of the Spanish Grand Prix grid.
The Brackley-based marque were so dominant around Barcelona's Circuit de Catalunya that third-on-the-grid Daniel Ricciardo in his Red Bull was a full second down on Hamilton, who grabbed the 35th pole of his F1 career.
Williams' Valtteri Bottas starts fourth, followed by a superb effort from Romain Grosjean to haul his Lotus up to a season-high fifth.
Kimi Raikkonen will start ahead of Ferrari team-mate Fernando Alonso, with the duo sixth and seventh respectively, followed by Jenson Button in his McLaren in eighth, with Williams' Felipe Massa ninth.
As for Sebastian Vettel, after missing most of Friday practice due to a wiring loom problem, the reigning four-times champion bowed out of qualifying a few minutes into the top-10 shoot-out to continue his weekend of woe.
"I've no drive," complained Vettel, who pulled over at turn three and will start 10th, resulting in an over-the-radio apology to Hamilton as he held up the Briton on his first attempt at a hot lap.
Vettel's problems, with eight minutes of the 12 remaining in Q1, resulted in red flags appearing for a second time during qualifying following Pastor Maldonado's crash in Q1.
Nico Hulkenberg and Sergio Perez will line up 11th and 12th for Force India, with Toro Rosso's Daniil Kvyat 13th for Toro Rosso, followed by Esteban Gutierrez in his Sauber.
Kevin Magnussen will start 15th as a technical issue with his McLaren prevented him from a making run in Q2, similarly with Toro Rosso's Jean-Eric Vergne - who qualified 16th.
The Frenchman, however, has a 10-place grid penalty against his name and will now drop to 21st, rather than the back of the grid, thanks to Maldonado.
Q1 was disrupted by a shocking error from the Lotus driver, who won this race two years ago for Williams but will start 22nd and last for the second successive grand prix.
In China, Maldonado failed to even make it out of the garage due to his car sustaining an oil leak and was forced to line up 22nd.
In Barcelona, the 29-year-old ran wide on to the astroturf on the outside of turn three, sending him into a spin into a wall where he lost the front-right wheel.
Ahead of the back-row pairing of Vergne and Maldonado will be Adrian Sutil in his Sauber in 16th, followed by Marussia duo Max Chilton and Jules Bianchi, with Caterham pair Marcus Ericsson and Kamui Kobayashi 19th and 20th.
Chilton's time, however, of 1:29.586 would only have been good enough for fourth on the grid in the GP2 support race at this track.
Rosberg had been quickest in the first and second sessions, with Hamilton complaining over the radio during the initial run the car was "a nightmare to drive" and the team had made it "worse".
But despite further adding the car was "a real handful", the 29-year-old still managed to claim pole.
"It's been a tough day," said Hamilton.
"Nico drove well in final practice and again through the first two sessions of qualifying.
"But right at the end I eked out everything and more from the car, and I'm overwhelmed. I'm so happy."
Hamilton, who has not won at this track in seven previous visits, added: "There are lots of circumstances as to why that's happened, but I've not been fast enough.
"In the past it's not been my time, but tomorrow I'll do my best to bring some really good points for the team and (ensure) it ends positively."
Rosberg said he was "very disappointed" at again coming second to Hamilton, something he claimed he does not "particularly enjoy".
The German added: "In the end I put in a good lap, but Lewis did a better job.
"It's still all to play for. All it takes is a good start and I'm back in the lead again."
Although the best of the rest, Ricciardo knows being a second off the pace of Mercedes is "not good enough".
Ricciardo added: "I was expecting a smaller gap.
"We've made improvements, but so have Mercedes, and for sure we want to get closer to the front two."