Abstract Modified poly(vinyl acetate) copolymers with drying oils as comonomers have been prepared. The unsaturated triglycerides can produce cross-linking and give a waterproof effect due to their hydrophobicity. The new copolymers synthesized by solution polymerization in an organic medium have been submitted to analytical characterization in order to investigate the role of the drying oils in the polymerization reaction. NMR spectroscopy has been used to obtain information on the structure of the polymerization products and to confirm the eventual C-C bond formation between vinyl acetate and triglycerides. Spectroscopic data are found to be in agreement with copolymer formation.