In order to recycle TiO2 photocatalysts and prevent TiO2 from damaging polyvinylidene fluoride (PVDF) films, porous ZrxSi1-xO2 shell/void/TiO2 core particles (Zr-SVTs) were firstly synthesized by the synergistic effect between nonionic surfactant P123 ((EO)(20)(PO)(70)(EO)(20)) and oleic acid (CH3(CH2)(7)CH = CH(CH2)(7)COOH) and cohydrolysis between TEOS and ZrOCl2 center dot 8H(2)O, and then embedded them into PVDF to prepare PVDF photocatalytic films (Zr-SVTP films) by phase inversion process. Zr-SVTs were characterized by SEM, TEM and EDX while Zr-SVTP films were characterized by SEM. The preparation condition and recycle of Zr-SVTP films were investigated and determined. The photocatalytic activities of Zr-SVTP films were investigated by cleaning oily wastewater. The results show that Zr-SVTs hold porous characteristic, and Zr-SVTP films perform the better photocatalytic activities compared with PVDF films (SVTP) embed by SiO2 shell/void/TiO2 core without doping Zr in SiO2 shell, this is because the mass transfer inside channels of Zr-SVTs is promoted by ZrxSi1-xO2 shell, ensuring the better photocatalytic activities of Zr-SVTP films. Therefore, Zr-SVTP films structure characteristic will have a promising application in recycle of TiO2 photocatalysts and cleaning oily wastewater. (C) 2015 Elsevier B.V. All rights reserved.