Nanostructured palladium-copper electrocatalysts with Pd:Cu ratios of 1:3, 1:1, and 3:1 were synthesized using a Sacrificial Support Method (SSM) in combination with the thermal reduction of metal precursors. The materials were comprehensively characterized by X-ray diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Scanning and Transmission Electron Microscopy (SEM and TEM), surface area measurements (Brunauer-Emmett-Teller, BET) and Differential Electrochemical Mass Spectroscopy (DEMS). The SSM method enables the preparation of nano-sized unsupported Pd-Cu catalysts with uniformly-distributed particles and high surface area, in the range of 40 m(2) g(catalyst)(-1). Their catalytic activity for the electrooxidation of several alcohols (methanol, ethanol, ethylene glycol and glycerol) was investigated in alkaline media. In situ Infrared Reflection Adsorption Spectroscopy (IRRAS) and Density Functional Theory (DFT) calculations were used in order to understand the mechanism of the various alcohols electrooxidation reactions. (C) 2016 Elsevier B.V. All rights reserved.