A series of bimetallic Pd-Ni thin films with different compositions were prepared on glass carbon electrodes (GCEs) by a template-free, double-potential step electrodeposition technique and their compositions were controlled well by adjusting electrodeposition conditions, such as the concentration ratio of palladium ions to nickel ions in electrolytic solutions, nucleation time and growth time. SEM observations and EDS analyses demonstrate that the structural feature and compositions of the as-prepared Pd-Ni films varied with deposition conditions. Electrochemical characterizations indicate that electrochemical properties and electrocatalytic activity of the bimetallic Pd-Ni thin films were strongly dependent on the composition, structure and surface morphology obtained under different deposition conditions. The high catalytic activity and the low cost of the Pd-Ni films enable them to be promising electrocatalysts for the oxidation of methanol and ethanol in alkaline media. (c) 2009 Elsevier B.V. All rights reserved.