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M'Bala Nzola was both hero and villain for the hosts, giving them an unexpected lead in the 66th minute but missing their fourth kick of the shootout.
PSG reserve goalkeeper Matvei Safonov then saved Andy Diouf's spot kick to hand his side the victory with all of their penalty takers scoring with their first four.
"I'm happy. I don't think I'm the man of the match. Stopping penalties is normal for a goalkeeper," Safonov told beIN Sports. "It was a tough game against a very good team."
The Parisians had looked dominant for much of the contest but briefly found themselves behind before Goncalo Ramos levelled in the 70th minute.
"We're very happy with the win, but it wasn't the match we wanted. We were level 1-1 after 90 minutes," PSG left-back Nuno Mendes said.
