Johan Edfors had a 64, while Paul Lawrie, Oliver Wilson, Nick Dougherty, Robert Rock, Shiv Kapur, Jamie Donaldson and Roop Kakko were in a group three shots behind the leader.
John Daly, who finished second at the Italian Open on Sunday, birdied the last hole for a 68. He expressed relief that the wind didnt blow on the seaside course after battering players in two days of practice.
It was cold and rainy, Daly said. I dont think Id have broken par the other two days, but the lack of wind made it easier.
Rory McIlroy shot 69, while playing partner Colin Montgomerie had a 70. Darren Clarke had a 71 and Padraig Harrington shot 73.
Molinari made a 30-footer for eagle at the long third hole, and another at the 13th.
The 20-year-old McIlroy started slowly with two bogeys on his first three holes but, played the last 10 in five under.
My game did not feel comfortable but I got round in three under, so Im not out of it, he said.
Daly sprayed some tee shots, but a 7-iron got him out of the rough at the first and he saved par.
I feel like Im doing better with the putter. I chipped and putted pretty good, said Daly, playing his third tournament in Europe while serving a six-month PGA Tour suspension.