Molinari triumphed in the event 12 months ago - to add to his victory in his 'home' tournament from 2006 - and he's made a great start as he looks to defend his title.
The 34-year-old was among five players who carded rounds of 64 to end the day seven under as Alexander Bjork, Jamie Donaldson, Kiradech Ariphbarnrat and Eddie Pepperell also impressed at the top of the leaderboard.
Molinari knows there is plenty of work to be done over the remaining three rounds but he was delighted with his fast start.
He said: "It was great to get off to a good start, but there's still a lot of hard work to be done, it was great to see so many people out on the course getting behind me."
In a competitive field, two players are on -6, one shot off the co-leaders, with Byeong Hun-An and George Coetzee signing for rounds of 65, while Alex Noren, Chris Paisley and Mathieu Pavon are a further shot back on -5.