Mercedes, this season's one-lap specialists, locked out the front row for the second consecutive race, with Rosberg starting from pole for the third successive time.
Rosberg pipped Hamilton by just 0.091secs, and now has the chance to follow in the footsteps of father Keke exactly 30 years on and become a winner around the streets of the principality.
Whilst the statistics may look bad for Mercedes new-boy Hamilton, who was expected to comfortably outshine close friend Rosberg upon his arrival at the team earlier this year, on this occasion he had no qualms about being second best.
"I've been struggling all weekend with the car, my pace sucking," bemoaned Hamilton, who won this race in 2008 en route to claiming the title.
"It's the first time I've ever had that experience here in Monaco, since 2005 (when he was in Formula Three).
"I've always been on it, I've not had any problems with confidence or anything like that, but this weekend has been difficult.
"My last lap is probably the first time I've switched my tyres on all weekend, and when you don't generate the heat in your tyres you don't have the confidence to hit the brakes hard and brake late.
"Even on that lap my tyres weren't ready by turn one, which means you have a bit of understeer and you're playing catch-up for the rest of the lap.
"But generally the rest of the lap was great. That's why my middle and last sectors were competitive.
"It was a big improvement for me because in P1, P2 and P3 it was a disaster.
"I think it's because it's still a new car, and for whatever reason I'm still coming to terms with it.
"So I'm really happy to be here, to lock out the front row for the team. It was a massive improvement for me, so I'm chuffed."
It was in 1983 Keke Rosberg triumphed in Monaco in a Williams-Ford, leaving Nico with the opportunity of becoming the first son of a winner at this track to follow suit.
The younger Rosberg, however, is still far from counting his chickens given how he has only finished ninth and sixth from pole at the last two races in Bahrain and Spain.
That is despite the fact a clean start for the Mercedes duo should allow them to control the race from the front.
"It's always nice to hear these statistics, but it doesn't really change much for tomorrow," said Rosberg.
"Obviously I'm very happy to be starting first. Everything went to plan and the last lap was okay.
"So it's great to be on pole again, especially in Monaco. If you want to do that at any track then it's this track where it makes a difference.
"But in Barcelona (Spanish GP) we struggled a lot in the race. I was 70 seconds behind at the end of the race from the winner (Fernando Alonso).
"We're improving, but it's still difficult to understand the tyres and get the most out of them, so there are still a lot of question marks remaining.
"Here, I'm sure we've made a step forward, but it's still going to be difficult for us tomorrow, definitely.
"It's still our weakness, but we'll make the best of it, and who knows? You can always have a few surprises."
Red Bull occupy the second row, with reigning triple world champion Sebastian Vettel ahead of team-mate Mark Webber.
For Vettel, although third on the grid, it is still a relief as title rivals in Lotus' Kimi Raikkonen and Ferrari's Alonso - four points and 17 points adrift respectively - line up fifth and sixth.
Jenson Button starts ninth in his McLaren, two places behind team-mate Sergio Perez, primarily due to an issue at the start of his final hot lap when his car lost power.
Paul Di Resta failed to even make it out of Q1 and is 17th on the grid, equalling the worst slot of his career going back to the 2011 Belgian GP.
That, however, was the fault of Force India as they failed to call in the Scot for a fresh set of intermediate tyres given qualifying had started in the wet.
Marussia's Max Chilton is 20th, with Felipe Massa last as Ferrari failed to repair his car in time following an accident in final practice.
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