The direct methanol fuel cell is an emerging energy conversion device for which Pt is considered as the state-of-the-art anode catalyst. Herein, we show that the activity and stability of Pt for methanol oxidation can be significantly enhanced using Mo-doped CeO₂ (Ce_1−xMo_xO_2−δ) solid solutions as co-catalysts. X-ray photoelectron spectroscopy (XPS) reveals a strong electronic interaction between Ce_1−xMo_xO_2−δ and Pt in Pt/Ce_1−xMo_xO_2−δ–C catalysts. Among all Pt/Ce_1−xMo_xO_2−δ–C catalysts, the catalyst with a Ce/Mo atomic ratio of 7/3 (Pt/Ce_0.7Mo_0.3O_2−δ–C) exhibits the highest activity, up to 1888.4 mA mg_Pt⁻¹, which is one of the best results reported so far. A direct methanol fuel cell incorporating the Pt/Ce_0.7Mo_0.3O_2−δ–C as the anode catalyst exhibits a maximum power density of 69.4 mW cm⁻², which is 1.8 times that of an analogous fuel cell using the commercial Pt/C-JM as the anode catalyst.