Stilbene phytoalexins are specialized metabolites present in numerous plants. They play an important role in plant environment adaptation, especially in plant defense and signaling. Moreover, they have attracted attention of cosmetic and pharmaceutic sectors thanks to their biological activities (e.g., antiradical, anticancer properties). From the core resveratrol, a wide variety of oligomers are characterized from plant extracts or vegetal cell cultures. Nevertheless, very low quantity of a stilbene mixture can be recovered from a quite large amount of biomass. To decipher the role of these various compounds, pure synthetic molecules in sufficient amount are required. However, literature survey proves the lack of synthetic methodologies and especially of methodologies applying green chemistry principles. The GlycoStil ANR project aims to develop sustainable strategies for the synthesis of stilbene oligomers derived from resveratrol and piceid, the 3-O-glucoside of resveratrol.2,3 Oxidative coupling, mediated by an oxidase or silver acetate, was applied under various conditions to influence the selectivity of the reaction (Scheme 1). This strategy has allowed (i) the production of δ-viniferin, leachianol, labruscol, δ-viniferin diglucoside and ethyl oxystilbenin in quantity compatible with evaluation properties (>100 mg), and (ii) characterization of new dimers including iso-δ-viniferin and iso-ε-viniferin as well as several oxystilbenins