CuO/V2O5/FTO composite nanofibers photoelectrode was fabricated by electrospinning method with polyvinyl pyrrolidone(PVP) as fiber skeleton, copper(II) nitrate hydrate and vanadium(IV) -oxy acetylacetonate as raw materials. The structure of the samples was characterized by thermogravimetry. differential thermal analysis(TG-DTA), X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electronic microscopy(TEM) and X-ray photoelectron spectroscopy(XPS). The photoelectrocatalytic performance of the samples was analyzed by the degradation of methylene blue(MB) solution. The results show that the heterojunctions between CuO and V2O5 were formed, and the separation of photogenerated electron. hole pairs on CuO/V2O5/FTO was promoted, which made the degradation rate of MB catalyzed by CuO/V2O5/FTO much higher than that catalyzed by pure V2O5/FTO. The different molar ratios of n(Cu)/n(V) had influence on photoelectrocatalytic activity, and the CuO/V2O5/FTO with n(Cu)/n(V) = 1 : 1 had the highest catalytic activity(degradation rate of MB was 96%).