The preparation and research of nanometer metal oxides has drawn considerable attention because of their special structure and excellent chemical properties, particularly titania and titanium dioxide composite nanomaterials. A three-dimensional (3D) multiple-unit semiconductor CuO/TiO2 film was successfully synthesized by the combination of an electrospinning method and a hydrothermal reaction. The samples were characterized by differential thermal analysis (TG-DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM), which indicated that the diameter of TiO2 fibers was about <100 nm; moreover, the CuO nanoparticles or nanoplates were growing aslant on the surface of the TiO2 fibers, which led to the porous morphology for the hierarchical heterostructure. The photocatalytic property of the sample was tested via rhodamine B degradation and the sample showed the obvious catalytic activity for the degradation of the simulation of pollutants. Furthermore, the photocatalytic mechanism of the CuO/TiO2 nanofiber is expounded at the end of the study.