This comparative study characterizes two types of metallic and core-shell bimetallic nanoparticles prepared with our modified polyol method. These nanoparticles consist of Pt and Pt-Pd core-shell nanocatalysts exhibiting polyhedral morphologies. The controlled syntheses of Pt metallic nanoparticles in the 10-nm regime (4-8 nm) and Pt-Pd bimetallic core-shell nanoparticles in the 30-nm regime (15-25 nm) are presented. To realize our ultimate research goals for proton exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs), we thoroughly investigate the dependence of the electrocatalytic properties of the nanoparticles on the structure, size and morphology. Significant differences in the electrocatalysis are also explained in experimental evidences of both Pt and Pt-Pd nanocatalysts. We suggested that the core-shell controlled morphologies and nanostructures of the Pd nanoshell as the Pd atomic monolayers will not only play an important role in producing inexpensive, novel Pt- and Pd-based nanocatalysts but also in designing more efficient Pt- and Pd-based nanocatalysts for practical use in DMFC technology. Our comparative results show that Pt-Pd nanocatalysts with Pd nanoshells exhibited much better electrocatalytic activity and stabilization compared to Pt nanocatalysts. Interestingly, we found that the size effect is not as strong as the nanostructuring effect on the catalytic properties of the researched nanoparticles. A nanostructure effect of the core-shell bimetallic nanoparticles was identified. (C) 2011 Elsevier Ltd. All rights reserved.