Novel copolymers of vinyl acetate and dialkylfumarates, poly(VA-co-DRF) with R = isopropyl (DIPF) or octan-2-yl (DOF), were synthesized by radical copolymerization under microwave conditions. The products were characterized by ¹H NMR and FTIR spectroscopies, size exclusion chromatography and differential scanning calorimetry. Based on these copolymers three membranes supported on polyvinyl alcohol were prepared and their morphology, swelling and mechanical properties were studied. The swelling kinetic was analyzed and interpreted in light of the Fick transport model, showing that the water transport occurs through a non-Fickian diffusion mechanism. The results show that the membrane prepared of poly(VA-co-DOF) exhibited excellent properties as potential platform for transdermal delivery system: they exhibited good tensile strength, moderated swelling and form thin and transparent films.