Catechins (flavanols) are strong antioxidants, free radical scavengers and inhibitors of lipid peroxidation. New bio-based antioxidant compounds obtained by depolymerization of plant polymeric flavanols (procyanidins) in the presence of cysteine or cysteamine, as well as their underivatized counterpart, (-)-epicatechin, were evaluated in terms of their percutaneous absorption profiles taking into account their free radical scavenging efficiency. The evaluation of the percutaneous absorption of flavanols was carried out by an in vitro methodology using both pig and human skin. A good correlation was obtained using both skins in the evaluation of the skin absorption profiles. It can be deduced that 4beta-(S-cysteinyl)epicatechin (Cys-Ec) has a tendency to be located mainly in the outermost layers of the skin, whereas 4beta-(2-aminoethylthio)epicatechin (Cya-Ec) has a pronounced percutaneous absorption capacity. Their antioxidant properties and their skin penetration profiles support their potential cosmetic or pharmacological applications.