Francesco was at 10-under 206 to move ahead of his older brother, who had a 69.
Oliver Wilson (68) and Simon Dyson (70), Gregory Bourdy (70) and Julien Guerrier (73) of France and Stephen Gallacher (71) of Scotland were another shot back.
The sibling rivalry could put pressure on European Ryder Cup captain Colin Montgomerie to make sure the duo, a winning pair at golf’s World Cup in China last year, both debut against the United States at Celtic Manor in October.
Francesco has qualified, but Edoardo would only make the team as a captain’s pick when Montgomerie fills out his squad Sunday.
Edoardo has stiff competition from four Europeans based on the PGA Tour — Justin Rose, Padraig Harrington, Luke Donald and Paul Casey — who are all ranked among the world’s top 22 players and hoping to receive one of Montgomerie’s three captain’s picks to extend their Ryder Cup careers.
Montgomerie acknowledged that he’d have a dilemma if Edoardo were to win his second title in Scotland this year after a victory at Loch Lomond last month.
“… It would make my headache even worse,” Montgomerie said. “It’s a lovely headache to have. I’ve got guys on form and the guys in the Fedex Cup are doing well. They all made the cut and it will be interesting to see how they get on.”
He admitted that pairing the Molinaris would be an attractive option to have.
“Even at this stage, that’s a great advantage to have,” Montgomerie said. “I’m not just picking the best players right now, I’m picking who can play with whom. So, of course, it’s a criterion because Francesco’s brother is the obvious candidate.”
The fourth round of the Johnnie Walker also could alter the makeup of the nine players who automatically earn places on the European team, with both Sweden’s Peter Hanson and Spain’s Miguel Angel Jimenez in danger down the qualifying table.
In Paramus, New Jersey, Jason Day had three late birdies in a 4-under 67 on Friday and he held a one-stroke lead after two rounds in The Barclays.
Nine players had at least a share of the lead at some point during the second round until Day’s late surge. He was at 8-under 134, one shot clear of Kevin Streelman (63) and Vaughn Taylor (70) going into the weekend of the FedEx Cup’s first playoff event.
Tiger Woods missed a 20-inch par putt on the fifth hole and wound up with a 73, eight shots worse than his opening round.
The good news for the world’s No. 1 player — he will stay atop the world ranking for at least another week after Phil Mickelson missed the cut.
Streelman ran off six birdies in a seven-hole stretch at the Ridgeway Country Club course.
Stewart Cink raised his Ryder Cup hopes with a 69 that put him in a group at 6-under 136 with Martin Laird (67) and John Senden (69).
In Winnipeg, Manitoba, Michelle Wie shot a 3-under 69 to stay atop the leaderboard halfway through the Canadian Women’s Open.
She posted a two-round total of 10-under 134, three strokes ahead of Jiyai Shin of South Korea, who had a second-round 67.
Morgan Pressel had a 66 at the St. Charles Country Club to move into a tie at 138 with defending champion Suzann Pettersen of Norway.
Sarah Jane Smith of Australia also had a 66 and was in a group at 3 under in the tournament with a $2.25 million purse.
Shin is ranked No. 4 on the World Rolex Rankings and has nine top-10 finishes this season.
The field dropped to 154 players after Shi Hyn Ahn and Il Mi Chung of South Korea were disqualified late Thursday for mistakenly playing each other’s balls on the 18th green.