Heterostructured NiO/ZnO composite nanofibers were prepared by electrospinning technique employing polyvinyl alcohol (PVA) and Zinc acetate as precursors and then solvothermal growth of NiO nanostructures on as-electrospun ZnO nanofibers substrate. The morphology and structure of NiO/ZnO composite nanofibers were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), high-resolution transmission electron microscope (HRTEM) and PL spectra. Photocatalytic activity was tested via rhodamine B (RB) degradation as the model reaction. The results showed that the as-fabricated sample were composed of NiO nanoparticles assembling uniformly on the surface of ZnO nanofibers to form NiO/ZnO heterostructures. Compared with the pure ZnO nanofibers, NiO/ZnO composite nanofibers exhibited enhanced photocatalytic activity in the decomposition of RB under ultraviolet light. This material also shows good catalytic stability and the decolorizing efficiency of RB solution remains as high as 89% after 3 times recycle. Moreover, it is easily separated, removed from the system after reaction and reuse.