PVP/ZnO-TiO2 composite nanofibers were fabricated through a combination of sol–gel and electrospinning methods using polyvinglpyrrolidone ( PVP) as starting materials. ZnO-TiO2 nanofibers of 100–200 nm diameter were obtained by high temperature calcinations of the inorganic organic PVP/ZnO-TiO2 composite fibers.The materials were characterized by DSC- TGA, FT-IR and SEM. The process of the photocatalytic degradation of methylene blue using ZnO-TiO2 nanofiber as catalyst was investigated. The results show that the ZnO-TiO2 nanofiber dopped 3% ZnO has the highest photocatalytic activity for methylene blue degradation, the degradation rate of methylene blue solution reached 99% under sunshine for 6 h., and it’s still 95% after eight times reuse.