The electrochemical behaviour of Pt-decorated unsupported Ru catalysts-based anodes has been investigated in direct methanol fuel cells (DMFCs). A preparation procedure allowing the surface decoration of unsupported Ru catalysts by Pt nanoparticles has been developed. DMFC power densities of 150 mW cm −2 at 130 °C have been achieved with ultra-low Pt loading anodes (0.1 mg cm −2) under air feed operation. Adsorbed methanolic residues stripping voltammetry analysis has been carried out to get information on the electrocatalytic activity of the Pt-decorated anodes in relation to the state-of-art carbon supported Pt–Ru (1:1) alloy and bare unsupported Ru catalysts.