The consumption of fruit and vegetables (F&V) is inversely associated to the development of cardiovascular diseases, several kinds of cancers and other chronic diseases. Moreover, the cardiovascular protection could be ascribed to flavonoids, a class of polyphenols largely distributed in F&V. Polyphenols are poorly absorbed from the gastrointestinal tract (GIT) and undergo extensive metabolization by colon microflora before reaching plasma. Thus, before their absorption, polyphenols could exert a health benefit directly in the GIT. As a matter of fact, they were shown to protect polyunsaturated lipids from oxidation during gastric digestion. The bioaccessibility of polyphenols, defined as their release from the food matrix and solubilization into the bolus, is a prerequisite step.