WENTWORTH, United Kingdom, May 24, 2013 (AFP) - Molinari shot a second round 68, four-under par, to head the field after making four birdies in his last eight holes to be sitting pretty in the clubhouse by lunchtime.
A cluster of players finished a shot back from Molinari, whose brother Edoardo was two-under, including South Africa's George Coetzee, Marc Warren of Scotland, Mark Foster from England and Spain's Alejandro Canizares.
A grandstand finish from English youngster Eddie Pepperell, who birdied the last four holes, got himself to four-under alongside another Italian, Matteo Manassero.
The deteriorating weather meant few players were likely to challenge Molinari's mark at the top of the leaderboard in the afternoon and Graeme McDowell, Rory McIlroy, Ian Poulter and defending champion Luke Donald all failed to make the weekend.
The cut fell at two-under par and Justin Rose birdied the par-5 18th to just get in on the mark but 75s for McIlroy and McDowell scuppered their chances.
The pair finished on 149, five over par with another Ryder Cup player, Paul Lawrie two shots better off on 147 but still heading home.
Lee Westwood, however, was another early finisher who made the cut easily finishing on three-under par, the same score as Ernie Els and the winner here in 2010, Simon Khan.
McIlroy missed the cut here last year and never looked happy in miserable rainy conditions.
McIlroy said: "I just was grinding and I didn't play particularly well.
"I couldn't give myself any chances to get any shots back and try to get in at the weekend. It was not the weather you expect in London in May but it was the same for everyone and some guys deal with it better than others."
Molinari was one of the few to get a score going in the downpour and is in good shape to bid for a fourth win on the European Tour.
"Six-under is a good score given the conditions and it is a great position going into the weekend. But it is a very tough golf course so anyone even six or seven shots behind is still in it. It is the right time of year to be in good form and hopefully it keeps going that way," said Molinari.
Donald's exit after winning here the last two years was one of the biggest shocks of the day but he paid the price for his first day 78 although he claimed he is close to his best form.
Donald said: "I made five birdies today so it is not like I am a million miles away. It is doing the things that Luke Donald does well - be tidy around the green and make those putts when I need to.
"I am not too worried. It is never nice to miss a cut, especially here at Wentworth, a place I have played well. I will be back - failure is a much bigger motivator for me than success."
Poulter shot 76 for the second day on a course where he has never had much success.
"It is horses for courses and I guess this isn't my course," he said.
Leading and selected scores after the second round of the European PGA Championship here at Wentworth on Friday (GB/IRL unless stated, par 72):
138 - Francesco Molinari (ITA) 70-68
139 -Alejandro Canizares (ESP) 69-70, George Coetzee (RSA) 69-70, Mark Foster 70-69, Marc Warren 69-70
140 - Eddie Pepperell 71-69, Matteo Manassero (ITA) 69-71
141 - Ernie Els (RSA) 72-69, Lee Westwood 70-71, Simon Khan 69-72, Gregory Havret (FRA) 70-71, Shane Lowry 70-71, Niclas Fasth (SWE) 70-71
142 - Nicolas Colsaerts (BEL) 72-70, Richard Bland 71-71, Raphael Jacquelin (FRA) 71-71, Phillip Price 73-69, Lee Slattery 71-71, Edoardo Molinari (ITA) 71-71, Jason Levermore 72-70
143 - Sergio Garcia (ESP) 72-71, Thomas Bjorn (DEN) 69-74, Gonzalo Fernandez-Castano (ESP) 68-75, Alvaro Quiros (ESP) 70-73, Mikko Ilonen
(FIN) 67-76, Wen-chong Liang (CHI) 75-68, James Kingston (RSA) 66-77
144- Anders Hansen (DEN) 70-74, Jaco Van Zyl (RSA) 75-69, Pablo Larrazabal (ESP) 71-73, David Drysdale 71-73, Graeme Storm 73-71, Darren Clarke 74-70, Martin Kaymer (GER) 70-74, Branden Grace (RSA) 71-73, Bernd Weisberger (AUT) 73-71, Gregory Bourdy (FRA) 71-73, Alessandro Tadini (ITA) 73-71
Selected others
145 - Ross Fisher 72-73, Peter Ulhlein (USA) 72-73, Thongchai Jaidee(THA) 74-71, Jbe Kruger (RSA) 71-74
146 - Colin Montgomerie 71-75, Jose Maria Olazabal (ESP) 75-71, Paul McGinley 71-75, Justin Rose 72-74
147 - Paul Lawrie 75-72
148 - Tom Lewis 73-75
149 - Rory McIlroy 74-75, Graeme McDowell 74-75
150 - Luke Donald 78-72
152 - Ian Poulter 76-76
155 - Michael Campbell (NZ) 77-78