Novel composite asymmetrical membranes based on poly(vinyl alcohol)-co-ethylene (EVAL) as the host material and new polyethers that contain azobenzene moieties in the side chain were prepared by dry-cast phase inversion after dissolving the azo polymers in tetrahydrofuran and EVAL in dimethylsulfoxide and subsequently mixing the resulting solutions. By taking advantage of the proper temperature variation in the oven used for solvent evaporation, asymmetrical membranes that exhibited a dense, crystalline layer on the bottom and a porous, mainly amorphous layer on the top were obtained. Remarkable changes in the surface morphology and the contact angle with water were observed on the top surfaces of the composite membranes. This was ascribed not only to the enhanced concentration of azo polymer on the top surface but mostly to a conformational change in EVAL induced by the photoisomerization of the guest azo groups, as shown by HRMAS (1)H NMR. The morphological and structural changes in EVAL could be reversed on exposing the membrane to visible light for 24 h.