A new kind of hollow titania spheres‐chitosan (hTiO2‐CS) hybrid membranes was prepared by a physical blending method. hTiO2 spheres were found to disperse well in the as‐prepared hTiO2‐CS hybrid membranes. Their incorporation can reduce the chitosan crystallinity and enhance slightly its hydrophilicity and thermal stability. Subsequently, hTiO2‐CS/PAN composite membranes comprising of the hTiO2‐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 90 wt % aqueous solution of isopropanol at 80 °C. This promising kind of composite membranes may find potential application in the dehydration of alcohols.