The Turin native was playing on his local course, in the Italian Open, and carded a second round of 67 finish on nine under par. He shares top spot on the leaderboard with Chile's Felipe Aguilar and Ireland's Simon Thornton.
Molinari, whose halved match with Tiger Woods ensured Europe won the Ryder Cup outright in the 'Miracle at Medinah', has been understandably the centre of attention all week as he bids to claim his national tournament for the second time. "It adds a little pressure," he said of the spotlight. "But it's good, it gives you an extra motivation to do well and get focused for 18 holes.
"I said at the beginning of the week that I didn't want to think of anything but just enjoy the week, try to make some birdies and I'll try to do the same Saturday and Sunday. It doesn't really matter that I won before; this is a special, special week for me.
"I was emotional yesterday on the 10th tee at 8am with only 50 watching so now with all these people on my course it's a great feeling. It has been brilliant so far so let's hope it continues over the weekend. You have to embrace it, have fun; I smile on the course when I see people I know. I know they are rooting for me so I just try to enjoy it."
His Ryder Cup teammate, Nicolas Colsaerts, had looked like he would retain his overnight share of the lead, but he bogeyed the 16th and 18th - where he duffed a chip - to return a 71 and finish eight under alongside Ireland's David Higgins and Steve Webster of England.
"It's always tough to follow a day of prime striking," said Colsaerts, who shot 65 on Thursday. "I missed only one green yesterday and everything was going my way pretty much. Then I started with a bogey today with a seven iron in my hand so that doesn't get you in the greatest of moods." Higgins has just one top-three finish to his credit in more than 200 European Tour events but added a 69 to his opening 67 and feels the course suits his game. "I didn't hit it as close as yesterday," said the player ranked 684th in the world. "But if you keep hitting the fairways on this course you can manage it and get a lot of opportunities and I am good at doing that. This is a good course for me, if I play well I have a chance. A lot of the other courses are very long and I am trying to hit it over corners, but this one is about hitting it down the middle and I'm good at that."
A clutch of Scots lie six shots off the lead. Gary Orr, Peter Whiteford, David Drysdale, Chris Doak, and Scott Jamieson all finished on three under par, setting up the probability that some home hopefuls will have familiar faces for company during tomorrow's third round.
Former Ryder Cup captain Jose Maria Olazabal, whose last European Tour win came in the Mallorca Classic eight years ago, is four off the lead on five under after adding a 68 to his opening 71 to lie five under par.
"Yesterday was a battling day," he said. "I didn't hit the ball well at all and just managed to get my way in with a decent score. I still made a few mistakes today but it was better."
Two-time US Open winner Retief Goosen is two under on his return after a four-month injury lay-off with a stress fracture to his back, but former Open champion David Duval missed the halfway cut by two shots.