Hollow porous structures of Pt-Pd bimetallic alloy possess unique compositional and structural superiorities for catalytic and electrocatalytic applications, and are thus anticipated to manifest novel properties and/or enhanced performance compared with their monometallic counterparts. Herein, a general electrostatic-attraction-directed layer-by-layer assembly approach has been developed for the construction of a novel type of hollow porous Pt-Pd alloy nanospheres (Pt-Pd HPNSs) using SiO2 nanospheres as templates. Moreover, the Pt-Pd HPNSs with controllable shell thickness are prepared and their comparative electrocatalytic performances toward methanol oxidation reaction (MOR) are investigated. It's found that optimized Pt Pd HPNSs manifests markedly enhanced catalytic activity and durability in comparison with both commercial Pt black and Pd black catalysts. (C) 2015 Elsevier B.V. All rights reserved.