C-doped porous spherical TiO2 was prepared by modified sol-gel method and hydrothermal method. Then, it was used as support to fabricate RuAg/TiO2-C catalyst for methanol oxidation. The structural and electrochemical properties of the RuAg/TiO2-C catalyst were characterized by XRD, TEM, EDS, XPS and electrochemical analysis. The experiment results showed that the deposition of RuAg and doping of C could improve the electrocatalytic activity of the RuAg/TiO2-C catalyst for methanol oxidation. The cyclic voltammograms of the RuAg/TiO2-C catalyst showed that there was a larger methanol oxidation peak current at 0.544 V with a peak current density of 5.8 mA/cm2. No oxidation peak of intermediates can be seen on the reverse scan in the cyclic voltammograms. The RuAg/TiO2-C catalyst showed higher catalytic activity and better anti-poisoning ability for methanol oxidation than the commercial PtRu/C catalyst. The enhancement was owing to the strong interaction between RuAg nano alloy and TiO2-C support.