CuO-SiO2 composite aerogels were prepared by sol method. TiO2 nanofibers with diameter of ~16 nm were successfully prepared by vapor-phase growth using CuO-SiO2 composite aerogels to fill TiCl4.The structure and photoelectric properties of the materials were characterized by XPS, UPS, UV-Vis DRS, PL and etc. Compared with the commercial TiO2 nanoparticles (P25), the prepared CuO-SiO2@TiO2 nanofibers show much lower fluorescence intensity and slower recombination rate of photogenerated election-hole pairs. Loading of CuO onto the nanofibers, the fluorescence intensity of the CuO-SiO2@TiO2 /CuO was further reduced, and the absorption of visible light was enhanced. The photocatalytic reduction of CO2 was carried out in the absence of sacrificial agent using a 300W xenon lamp as light source. The CuO-SiO2@TiO2 and CuO-SiO2@TiO2/CuO were used as photocatalysts, the methanol yield was1304.0 and 1589.0μmol/g-cat, respectively. TOF was 0.038and 0.046/h correspondingly. The cyclic experiments showed that the nanofibers had good photocatalytic stability. After 5 cycles, the retention rate of CuO-SiO2@TiO2/CuO was 94%, and the yield of methanol was 1472.0 μ mol/g-cat, TOF was 0.042/h.