Nano-sized binary and ternary alloys are synthesized by polyol process on Vulcan XC72-R support. Nanostructured binary Pt-Pd/C catalysts are prepared either by co-deposition or by depositing on each other. Ternary Pt-Pd-Ru/C catalysts are prepared by co-deposition. The structural characteristics of the nanocatalysts are examined by TEM and XRD. Their electrocatalytic activity toward methanol oxidation and CO stripping curves were measured by electrochemical measurements and compared with that of commercial Pt/C catalyst. The results show that the binary nanocatalyst prepared by depositing the Pt precursor colloids on Pd-Vulcan XC-72R are more active toward methanol oxidation than that of the co-deposited binary alloy nanocatalyst. The co-deposited ternary Pt-Pd-Ru/C nanocatalyst based membrane electrodes assembly shows higher power density compared to the binary nanocatalysts as well as commercial Pt/C catalyst in direct methanol fuel cell. Significantly higher catalytic activity of the nanocatalysts toward methanol oxidation compared to that of the commercial Pt/C is believed to be due to lower level of catalyst poisoning. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.