The Italian from the IAM Cycling team prevailed in a bunch sprint at the end of the 179.4km stage from Fontenay-le-Comte, beating Europcar's Bryan Coquard, Sacha Modolo (Bardiani Valvolde) and Nacer Bouhanni (FDJ) to the line.
It was Pelucchi's first win of the year and just the third of his career, following successes on French soil last year in the Quatre Jours de Dunkerque and the Ronde de l'Oise last year as a Europcar rider.
There was an early break featuring Kevin Reza (Europcar), Rony Martias (Sojasun) and the Italian Nicola Boem (Bardiani Valvolde) and they opened up a five minute lead following the first classified climb of the day.
ORICA-GreenEDGE and AG2R came to the front to help FDJ - with French champion Bouhanni in their ranks - and they were within touching distance when the peloton commenced four laps of the 6.7km finishing circuit.
The trio were finally caught 10km from home with a bunch gallop to the line then inevitable with the 24-year-old from Lombardy prevailing.
The 61st edition of the four-day UCI Europe Tour continues on Wednesday with a 93.6km road stage in the morning followed by a 6.8km time trial in the afternoon.
Seven World Tour teams are in attendance with AG2R La Mondiale, Argos Shimano, Katusha, Garmin-Sharp, RadioShack-Leopard and Saxo-Tinkoff joining FDJ.