In order to selectively adsorb hydrolyzed polyacryamide (HPAM) and remove oil from oily wastewater, TiO2/void/porous Al2O3 shell particles (TVAs) were designed and prepared though hydrolysis and calcination; subsequently, the TVAs were embedded into polyvinylidene fluoride (PVDF) to prepare composite films (TVAP films). As polymeric supports, TVAP films were employed to immobilize TiO2 powder. TVAs were characterized using SEM, TEM, FT-IR, BET while TVAP films were characterized by SEM. The results indicate that the particle size of TVAs is mainly distributed between 700 and 800 nm, coreshell structure has been successfully built. The removal rates of TVAP films prepared under the optimum synthesis conditions for oil and HPAM reach 69.70% and 60.20% respectively, performing attractive properties of mass transfer and adsorption. Therefore, TVAP films are desirable as suitable materials to clean oily wastewater. (C) 2018 The Society of Powder Technology Japan. Published by Elsevier B. V. and The Society of Powder Technology Japan. All rights reserved.