A new bioartificial polymeric material consisting of a bilayer of cellulose acetate and poly(vinyl alcohol) was successfully obtained by casting method. The material was characterized by Fourier transform infrared spectroscopy, contact angle, scanning electron microscopy, differential scanning calorimetry, gas permeability, water vapor permeability, and mechanical properties. The characterization indicates that two distinct and well‐differentiated surfaces were achieved without detriment to the bulk properties. The interaction between natural and synthetic polymers indeed enhanced the gas permeability as well as the water vapor permeability in comparison to the original components, although mechanical properties were not substantially boosted by the combination of both. Moreover, beyond the interface, there were no detected interactions between the polymers as can be evidenced by the presence of a unique T_g in the bilayer. The amalgamation of the relatively good mechanical properties with the two differentiated surfaces and the improvement of the permeability properties could indicate the potential of the material for being used in medicine.