Bouhanni at the double in Giro
France's Nacer Bouhanni celebrates on the podium after winning the 7th stage of the 97th Giro d'Italia, Tour of Italy, cycling race from Frosinone to Foligno (211km) on May 16, 2014 in Foligno - by Luk Benies
Bouhanni handed the French their first win in Italy's biggest race in three years after overcoming a late puncture during Tuesday's rain-hit fourth stage to triumph at the finish line.
On Friday's transitional 211km stage, the 24-year-old of the FDJ.fr team doubled his tally when he left Italian Giacomo Nizzolo and Slovenian Luka Mezgec with the minor placings. Matthews finished fourth.
After Mezgec had launched the final dash for the finish line, Bouhanni used a combination of sheer speed and tactical nous to squeeze past the Slovenian and on towards victory, with Nizzolo finishing runner-up half a wheel behind.
"There was a gap, and I somehow found my way through it," said Bouhanni.
Despite benefiting from the early exit of German ace Marcel Kittel, who won two stages in three days before abandoning due to illness, 2012 French champion Bouhanni's exploits have prompted praise from retired Italian legend Mario Cippollini.
"He's the archetypal sprinter, he's afraid of nothing," said Cipollini, who still holds the record of 42 Giro stage wins.
Matthews, a sprint specialist who rides for Orica, leads compatriot Cadel Evans (BMC), a favorite for overall victory, by 21sec overall ahead of Saturday's rolling eighth stage from Foligno to Montecopiolo, which ends after a 6.4km climb.
Before many of the race's major climbing difficulties, Evans is in a favourable position having seen pink jersey rival Joaquim Rodriguez (Katusha) crash out of the race with three broken ribs on Thursday.
Evans is a former Tour de France and world champion and his closest rival, Colombian Rigoberto Uran, is third overall at 1min 18sec behind Matthews.