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The bio-accessibility (the release of compounds from solid food matrices) of grape polyphenols using an in vitro model simulating gastro-intestinal conditions has been investigated. In vitro studies are needed to unravel factors affecting the release of antioxidants during digestion. The amount of bio-accessible polyphenols, flavonoids and anthocyanins increases during gastric digestion. The transition in the intestinal environment causes a decrease in all the analyzed classes of polyphenols followed by a renewal in the extraction of polyphenols and flavonoids but not of anthocyanins. The stability under gastro-intestinal conditions of pure phenolic acids, flavonoids and resveratrol has been analysed. Gastric digestion had no effect on any phenolic tested. Phenolic acids and resveratrol were degraded under pancreatic conditions whereas catechin and quercetin were not. Changes in antioxidant activity during digestion were correlated to the changes in polyphenols concentration as well as to the pH. Our results suggest that the gastro-intestinal tract may act as an extractor where polyphenols are progressively released from solid matrix and made available for the absorption or to exert their biological effects in the gastro-intestinal tract.