Hollow mesoporous tungsten trioxide microsphere (HMTTS) was synthesized by spay drying method and Pt/HMTTS were prepared and used as new electrocatalyst for methanol oxidation. The structure of HMTTS and Pt/HMTTS was characterized with scanning electron microscopy (SEM), tunnel electron microscopy (TEM) and X-ray diffraction (XRD), and its electrocatalytic activity toward methanol oxidation was investigated with cyclic voltammetry (CV) and chronoamperometry (CA). The characterizations from SEM, TEM and XRD show that the platinum particles with an average size of 5 nm have been successfully distributed on the surface of HMTTS. Cyclic voltammetry and chronoamperometry indicate that Pt/HMITS catalyst exhibits higher electrocatalytic activity and good stability during methanol oxidation in comparison to Pt/C and Pt/WO3 catalysts. Published by Elsevier Ltd.