Ricciardo won both Monaco races in 2010.
The Australian, who won and finished second last time out at Spa, will line up on the front row alongside the New Zealander Brendon Hartley (Gravity-Charouz).
"The laps I did in the Toro Rosso during F1 free practice didn't put me off at all," he said. "In fact, quite the opposite.
"We saw a major improvement in performance between the first and second set of tyres, the track conditions were getting better all the time and I really thought that group B was going to be quicker than us.
"Last year, I won here after starting from pole, so I hope to do the same again this year."
On the second row is Robert Wickens (Carlin) and Alexander Rossi (Fortec Motorsports).
With concerns over traffic on the twisty street circuit, the drivers were split into two groups.
Ricciardo and Wickens were in Group A, with Hartley and Rossi in Group B.
1 RICCIARDO Daniel AUS ISR 1:26.427
2 WICKENS Robert CAN CARLIN 1:27.075
3 KORJUS Kevin EST TECH 1 RACING 1:27.098
4 PANCIATICI Nelson FRA KMP RACING 1:27.288
5 PIC Arthur FRA TECH 1 RACING 1:27.487
6 VERGNE Jean Eric FRA CARLIN 1:27.537
7 ROSENZWEIG Jake USA MOFAZ RACING 1:27.658
8 NEGRAO Andre BRA INTERNATIONAL DRACO RACING 1:27.930
9 ZAMPIERI Daniel ITA BMV TARGET 1:28.430
10 BERTHON Nathanael FRA ISR 1:28.447
11 CANAMASAS Sergio ESP BMV TARGET 1:28.536
12 RAMOS Cesar BRA FORTEC MOTORSPORTS 1:28.697
13 DE JONG Daniel NED COMTEC RACING 1:30.144
1 HARTLEY Brendon NZL GRAVITY - CHAROUZ 1:26.464
2 ROSSI Alexander USA FORTEC MOTORSPORTS 1:26.469
3 COSTA Albert ESP EPIC RACING 1:26.743
4 CHAROUZ Jan CZE GRAVITY - CHAROUZ 1:26.816
5 NEBYLITSKIY Anton RUS KMP RACING 1:27.176
6 TAMBAY Adrien FRA PONS RACING 1:27.458
7 GRUBMULLER Walter AUT P1 MOTORSPORT 1:27.611
8 VAN DER DRIFT Chris NZL MOFAZ RACING 1:27.757
9 PENTUS Sten EST EPIC RACING 1:27.783
10 MOVE Daniil RUS P1 MOTORSPORT 1:27.871
11 RICHELMI Stephane MON INTERNATIONAL DRACO RACING 1:28.017
12 WEBB Oliver GBR PONS RACING 1:28.824
13 MCKENZIE Daniel GBR COMTEC RACING 1:29.152