The present work presents a method to encapsulate pre-synthesised Ru nanoparticles (NPs) by Pt using a polyol method without capping agents at various pH values (6, 7, 8 and 10). The structural and surface properties of the catalysts were characterised using X-ray diffraction, transmission electron microscopy, CO stripping, and energy-dispersive X-ray spectroscopy. The studies suggest that the pH during encapsulation of Ru by Pt plays an important role in controlling of shell composition. A core shell catalyst with an alloy shell was obtained at a pH of 6, whereas a monometallic Pt shell was obtained at a pH of 10. The core shell catalysts gave higher steady-state current for methanol oxidation: 10-fold higher for alloy shells and 5-fold higher for Pt-enriched shells compared to the pure Pt catalyst. It is suggested that the highest catalytic enhancement of the core shell catalysts is obtained through the bi-functional character that dominates the alloy shells rather than the ligand-effect-promoted Pt-enriched shells. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.