A new kind of hollow titania spheres-chitosan (hTiO(2)-CS) hybrid membranes was prepared by a physical blending method. hTiO(2) spheres were found to disperse well in the as-prepared hTiO(2)-CS hybrid membranes. Their incorporation can reduce the chitosan crystallinity and enhance slightly its hydrophilicity and thermal stability. Subsequently, hTiO(2)-CS/PAN composite membranes comprising of the hTiO(2)-CS hybrid membrane as separation layer and a polyacrylonitrile (PAN) membrane as support layer were fabricated. Compared to the CS/PAN membrane, all of them exhibit a much better flux and separation factor for a 90wt% aqueous solution of isopropanol at 80 degrees C. This promising kind of composite membranes may find potential application in the dehydration of alcohols.