Pd-Cu alloy with hierarchical porous network structure is prepared via a facile one-pot hydrothermal reaction, by using a mixed solvent of ethylene glycol and water as the reaction media, and the block copolymer Pluronic P123 as the structure-directing agent. The Pd-Cu alloy networks are constructed by hierarchically assembled nanorods as building blocks. The structure, porosity, surface chemical state and electrochemical properties of as-prepared Pd-Cu alloy are characterized and analyzed. Owing to the superior hierarchical porous network structure, the Pt-Cu alloy catalysts present remarkably enhanced catalytic performance toward formic acid oxidation, in comparison with the commercial Pd black. Copyright (C) 2016, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.