Multi-walled carbon nanotubes (MWCNTs) were functionalized via π − π interaction with benzyl mercaptan. The subsequent bonding of thiol groups with Pt offered strong adhesion of Pt nanoparticles on MWCNT surface. Thermal treatment was introduced as the essential step of the catalyst preparation. The structure and morphology of the resulting Pt/MWCNT composite were characterized by transmission electron microscopy and X-ray diffraction, the results show that Pt nanoparticles were highly dispersed and effectively adhered on MWCNTs. The excellent electrocatalytic activity of the Pt/MWCNT composite for the oxidation of methanol was demonstrated by cyclic voltammetry.