Bimetallic hollow PtAu sphere (H-PtAu) was prepared with TiO2 (titanium glycolate spheres) as a template in the presence of citric acid, and the template was removed during the formation of H-PtAu. The morphology and surface structure of H-PtAu were characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). The results show that the structure of hollow sphere is strongly dependent on the concenteration of citric acid. The H-PtAu with uniform size is well dispersed; the Pt shell thickness can be controlled by the amount of Pt precursor. Electrocatalytic activities of H-PtAu with different Pt/Au atomic ratios were investigated by cyclic voltammetry (CV) in 0.5 M NaOH + 0.5 M methanol aqueous sloution. Results show that H-PtAu catalyst has higher methanol oxidation activity than the commercial Pt/C (JM) catalyst, and the optimal Pt/Au molar ratio is 1.0.