TiO2 nanofibers with a diameter of 8~10nm were successfully prepared by vapor-phase growth with mesoporous SiO2 spheres as templates and TiCl4 as precursor. Furthermore, CuO/TiO2 nanofibers with a heterojunction structure were also prepared through impregnation method for visible-light driven reduction of CO2 to methanol. XRD, SEM, TEM, XPS, ultraviolet visible diffuse reflection(UV-Vis) and photoluminescence(PL) were used to characterize the crystal structure, morphology, chemical valence, visible light absorption intensity and electron-hole recombination rate, respectively. Compared to P25 and anatase TiO2 nanoparticles, TiO2 nanofibers show much lower fluorescence intensity and more stable photogenerated electron-hole pair. Loading of CuO onto TiO2 nanofibers may further reduce the fluorescence intensity and enhance absorption of visible light. Under the irradiation of 300W xenon lamp for 5h, the yields of methanol over CuO/P25 was 696μmol/g-cat, and further enhanced to 1791μmol/g-cat over CuO/TiO2 nanofibers, 165% higher than that over CuO/P25.