Porous TiO2/ZnO composite nanofibers have been successfully prepared by electrospinning technique for the first time. It was generated by calcining TiO2/ZnCl2/PVP [PVP: poly(vinyl pyrrolidone)] nanofibers, which were electrospun from a mixture solution of TiO2, ZnCl2 and PVP. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) analyses were used to identify the morphology of the TiO2/ZnO nanofibers and a formation of inorganic TiO2/ZnO fibers. The porous structure of the TiO2/ZnO fibers was characterized by N-2 adsoption/desorption isotherm. Surface photovoltage spectroscopy (SPS) and photocatalytic activity measurements revealed advance properties of the porous TiO2/ZnO composite nanofibers and the results were compared with pure TiO2 nanofibers, pure ZnO nanofibers and TiO2/ZnO nanoparticles. (C) 2010 Hai Ying Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.