Lewis Hamilton secured pole position by beating Mercedes teammate to the top spot in qualifying for the Bahrain Grand Prix.
The world champion made up for a mistake in his penultimate run to complete a superb final flyer to beat Rosberg by 0.077s.
The much-criticised qualifying format disappointed again, however, with several periods without cars on track, especially in Q2.
Williams duo Valtteri Bottas and Felipe Massa will start sixth and seventh respectively, the Finn qualifying just 0.002s ahead of his teammate.
Nico Hulkenberg wound up a strong eighth in the Force India, the German making the jump to Q3 by being the only driver to lap in the final minutes of Q2.
The second segment kicked off with a problem with the lights at the end of the pitlane, which were still on red even after the countdown clock had started moving - a marshal having to wave the green flags to allow the cars to get moving.
Hamilton, who had been trailing Rosberg all weekend, set a blistering lap in his first run, posting a a 1:30.039 to outpace the German by nearly half a second.
Daniil Kvyat was the first driver to be eliminated in Q2, the Russian over a full second slower than Red Bull teammate Daniel Ricciardo.
Jenson Button was next, the Briton outqualified by rookie teammate Stoffel Vandoorne, who put on a sensational performance in his first ever F1 qualifying session.
Button will start 14th, two places ahead of Vandoorne, the McLaren duo split by the Haas of Esteban Gutierrez.
Toro Rosso's Carlos Sainz will start 11th, behind teammate Max Verstappen and Romain Grosjean in the leading Haas.
Q2 also highlighted the flaws of the new qualifying system, as just a couple of cars took to the track during the final seven minutes of the session, the rest of the teams deciding to save tyres.
All the front-runners took to the track with supersofts straight away, with Vettel leading the Mercedes duo and teammate Raikkonen as the green lights went off.
Every driver, in fact, jumped onto the track with the softest tyre compound.
The first man to be knocked out was Sauber's Felipe Nasr, who made a mistake during his final flying lap.
Rio Haryanto was the second driver eliminated, the Manor driver in the pits when the clock reached zero.
Renault's Jolyon Palmer qualified in 20th position despite a late improvement, but Renault endured a dismal session as teammate Kevin Magnussen - already set for a pitlane start for a penalty - qualified in 19th.
Ahead of the Renault duo, Force India's Sergio Perez was 18th ahead of the second Sauber of Marcus Ericsson.
Pascal Wehrlein was the final man to be eliminated after a superb display by the German, who will start from 16th position in the Manor.
The under-fire format saw the action in Q1 came to an early finish, the bottom of the grid decided with over two minutes left on the clock.
|5||Daniel Ricciardo||Red Bull Racing||1:31.403||1:31.122||1:30.854||12|
|8||Nico Hulkenberg||Force India||1:31.987||1:31.604||1:31.620||15|
|9||Romain Grosjean||Haas F1 Team||1:32.005||1:31.756||9|
|10||Max Verstappen||Toro Rosso||1:31.888||1:31.772||9|
|11||Carlos Sainz Jr.||Toro Rosso||1:31.716||1:31.816||9|
|13||Esteban Gutierrez||Haas F1 Team||1:32.118||1:31.945||9|
|15||Daniil Kvyat||Red Bull Racing||1:32.559||1:32.241||9|
|16||Pascal Wehrlein||Manor Racing MRT||1:32.806||6|
|18||Sergio Perez||Force India||1:32.911||7|
|19||Kevin Magnussen||Renault F1 Team||1:33.181||3|
|20||Jolyon Palmer||Renault F1 Team||1:33.438||6|
|21||Rio Haryanto||Manor Racing MRT||1:34.190||3|