Rosberg secured back-to-back pole positions for the first time in his Formula One career as Mercedes locked out the front row ahead of the Spanish Grand Prix.
Mercedes have become this season's one-lap specialists as they have now taken pole at the last three races, although race pace has then left something to be desired.
On this occasion at Barcelona's Circuit de Catalunya, Rosberg beat team-mate Hamilton by a quarter of a second, with the duo the only two drivers to dip below one minute and 21 seconds for the lap.
The statistics do bode well, though, as 17 of the 22 drivers on pole for this race at this track have gone on to take the chequered flag.
And only once in those 22 races has a driver not won from the front row of the grid, that being Michael Schumcher from third in 1996.
Behind the Mercedes pair will be triple world champion Sebastian Vettel in his Red Bull, followed by Kimi Raikkonen in his Lotus, with home hero Fernando Alonso fifth for Ferrari.
Team-mate Felipe Massa starts ninth, as he was punished for impeding Mark Webber in Q2, and was therefore not allowed to keep hold of his sixth-place finish.
Lotus' Romain Grosjean will start sixth instead, with Webber seventh, followed by McLaren's Sergio Perez and Paul Di Resta for Force India just making the top ten.
Given McLaren's problems so far this season, and with team principal Martin Whitmarsh conceding before qualifying both cars would struggle to make Q3, Perez performed wonders to make the top 10.
The Mexican starts ninth, notably finishing ahead of team-mate Jenson Button who starts a miserable 14th, with half a second splitting the pair in Q2.
It is the 33-year-old's worst grid slot since last year's British GP when he started 16th.
The Toro Rosso duo of Daniel Ricciardo and Jean-Eric Vergne had high hopes of making Q3, but both missed out and will start 11th and 12th.
Force India's Adrian Sutil lines up 13th, with Button alongside him on the seventh row, followed by Sauber's Nico Hulkenberg.
It is not just McLaren enduring a miserable run at present as another F1 institution in Williams is also suffering.
Come the conclusion to the opening 20-minute session neither Valtteri Bottas nor team-mate Pastor Maldonado managed to make it out of Q1.
Rookie Bottas will start 16th, whilst Maldonado, who won this race a year ago from pole position for Williams' first victory for seven and a half years, miserably takes his place on the ninth row in 17th.
Behind them are Esteban Gutierrez, who also suffered a three-place grid penalty for impeding, as well as perennial backmarkers Marussia and Caterham, with the latter's Giedo van der Garde winning the battle of the quartet, starting from his highest grid slot of his rookie campaign in 19th.
Behind the Dutchman will be Marussia pairing Jules Bianchi and Max Chilton, the Briton just a quarter of a second behind the Frenchman, with Caterham's Charles Pic at the back.
Despite the delight in the Mercedes garage, both Rosberg and Hamilton are wary of suggesting they can follow up with a victory.
"It all went perfectly well in qualifying, and I'm really happy with that," said Rosberg.
"But we have to be cautious after what happened in Bahrain (with Rosberg ninth after starting fron pole).
"Everyone has been working really hard to understand the problems and to understand how to get the most out of the tyres as they are hugely complex.
"We were behind in Bahrain, but hopefully we have caught up now. I'm a little more confident for tomorrow.
"But the race is going to be a whole different thing given the challenge of the tyres."
Hamilton added: "As Nico said, we have to approach the race with caution.
"But congratulations to him, he did a great job, I'm really happy for him, but I'm also really happy for the team given the work that has been going on back at the factory."
Given Mercedes' race pace in practice appears to have been far from exceptional, Vettel could follow Schumacher's lead for a rare win at this circuit away from the front row.
"We've taken a different approach," said Vettel.
"We have only used the option (medium compound) tyres (saving the primes, hard compound), so whether that will help us in the race we'll have to wait and see.
"The tyres are a challenge, but I'm happy with the result."
Spanish Grand Prix Qualifying Grid
1. Nico Rosberg (Mercedes)
2. Lewis Hamilton (Mercedes)
3. Sebastian Vettel (Red Bull)
4. Kimi Raikkonen (Lotus)
5. Fernando Alonso (Ferrari)
6. Romain Grosjean (Lotus)
7. Mark Webber (Red Bull)
8. Sergio Perez (McLaren)
9. Felipe Massa (Ferrari)
10. Paul di Resta (Force India)
11. Daniel Ricciardo (Toro Rosso)
12. Jean-Eric Vergne (Toro Rosso)
13. Adrian Sutil (Force India)
14. Jenson Button (McLaren)
15. Nico Hulkenberg (Sauber)
16. Valtteri Bottas (Williams)
17. Pastor Maldonado (Williams)
18. Giedo van der Garde (Caterham)
19. Esteban Gutierrez (Sauber)
20. Jules Bianchi (Marussia)
21. Max Chilton (Marussia)
22. Charles Pic (Caterham)
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