Nonsolvent induced phase separation (NIPS) method using NMP/water system was adopted to prepare PVA/PVC thin films and were characterized by FTIR & FE-SEM analysis. Mechanical strength measurements indicated that an optimum composition of PVA/PVC has maximum tensile strength and might be due to the intercalation of viscous PVA into the stiff PVC matrix. Degree of swelling (DS) and water contact angle (WCA) measurements showed greater wettability of the films with increasing PVA content as is revealed from the higher film porosity and diminished contact angle. Pure water flux (PWF) and mean pore size were studied to determine the water permeation capacity of the film. Vapour permeability of various films was evaluated by using three different aliphatic alcohols viz. Methanol, ethanol and propanol. Barrier property and selectivity in permeation were studied for a particular PVA/PVC composition with moderate number and size of the pores which exhibited minimum permeation capacity.