The present X-ray photoelectron spectroscopic study on carbon-supported Pt, Pt-Cr, Pt-Co, Pt-Ni, Pt-Co-Cr and Pt-Co-Ni electrocatalysts suggests that while Pt-Cr/C, Pt-Co/C and Pt-Ni/C binary alloy electrocatalysts are surface rich in platinum, both Pt-Co-Cr/C and Pt-Co-Ni/C ternary electrocatalysts happen to be surface rich in base metals. Among these electrocatalysts, Pt-Co/C electrocatalyst is found to possess a minimum amount of platinum oxides. Accordingly, Pt-Co/C exhibits a higher electrocatalytic activity towards oxygen-reduction reaction in the solid-polymer-electrolyte direct methanol fuel cells.