Polyhydroxylated fullerenes (PHF) were prepared by the reaction of fullerene with NaOH in the presence of tetrabutylammonium hydroxide (TBAH) catalytic alkali method. PHF modified nitrogen doped titanium dioxide (PHF-N-TiO2) was synthesized by a sol-gel method using the PHF as-prepared. The morphology and composition of the PHF-N-TiO2 have been characterized. The photocatalytic performance of the PHF-N-TiO2 for catalytic reduction of CO2 was investigated. The results show that the PHF-N-TiO2 performs enhanced absorption in the visible light region, leading to improved visible photocatalytic activity for the catalytic reduction of CO2 at room temperature. The average production rate of CO is up to 5.560 μmol·g-1·h-1. The average production rate of CH4 is 0.789 μmol·g-1·h-1. It is believed that the combination of PHF modification and nitrogen doping improves the visible photocatalytic activity of TiO2.