The Dams driver's best laptime of 1:27.067 was a track record on the new configuration.
The Frenchman stole iSport’s Sam Bird’s thunder in the dying seconds of the qualifying session after the Brit looked set for pole position on the ten minute mark.
Bird, who was fastest during the morning's session, had slowly moved his way up the timing sheet, and set a best laptime of 1:27.384 with just minute to spare.
However, on his final lap, Grosjean put in his best effort and shattered Bird's dream of pole, and repeated his Abu Dhabi performance.
With this second pole position, Grosjean pockets another two points increasing his total to twelve points – the exact same number as Jules Bianchi at the top of the standings, leaving Saturday's feature race crucial for the title.
Imola – Qualifying session
1. Romain Grosjean Dams 1:27.067
2. Sam Bird iSport International 1:27.384
3. Michael Herck Scuderia Coloni 1:27.558
4. Jules Bianchi Lotus ART 1:27.676
5. Giedo van der Garde Barwa Addax Team 1:27.735
6. Josef Kral Arden International 1:27.834
7. Marcus Ericsson iSport International 1:27.872
8. Jolyon Palmer Arden International 1:27.898
9. Davide Valsecchi Team AirAsia 1:27.909
10. Mikhail Aleshin Carlin 1:27.988
11. Luiz Razia Team AirAsia 1:28.073
12. Andrea Caldarelli Ocean Racing Technology 1:28.093
13. Fabio Leimer Rapax 1:28.143
14. Oliver Turvey Ocean Racing Technology 1:28.151
15. Esteban Gutierrez Lotus ART 1:28.160
16. Stefano Coletti Trident Racing 1:28.194
17. Rodolfo Gonzalez Trident Racing 1:28.310
18. Max Chilton Carlin 1:28.332
19. Pal Varhaug Dams 1:28.357
20. Dani Clos Racing Engineering 1:28.373
21. Fairuz Fauzy Super Nova Racing 1:28.382
22. Johnny Cecotto Super Nova Racing 1:28.490
23. Charles Pic Barwa Addax Team 1:28.549
24. Julian Leal Rapax 1:28.644
25. Nathanael Berthon Racing Engineering 1:28.646
26. Luca Filippi Scuderia Coloni 3:54.107