A series of nanostructured Pd-Fe bimetallic thin films with the performance of fast and high-efficiency electrochemical reductive dechlorination were directly formed on glassy carbon electrodes (GCEs) through galvanic replacement of partial Fe nanoparticles by Pd(II) ions. The composition and morphology of such Pd-Fe thin films are strongly dependent on the sacrificial Fe film templates fabricated by a template-free, double-potential step electrodeposition technique. The size, shape and morphology of the Fe nanoparticles that constitute the Fe thin films can be controlled well by adjusting the concentration of Fe(2+) ions in electrolyte solutions. Due to the good synergistic effect between Pd and Fe, the as-prepared Pd-Fe thin films with the novel microstructure display a high reactivity towards the electrochemical reductive dechlorination of carbon tetrachloride (a), which closely related to the composition of Pd-Fe thin films, applied potential and temperature. The dechlorination reaction of CT complied with pseudo-first-order kinetics. (C) 2011 Elsevier B.V. All rights reserved.