Nanostructured copper/multi-walled carbon nanotube (Cu/MWCNT) films have been fabricated by means of pulse electrodeposition in an acidic plating bath containing copper sulfate and purified MWCNTs. The influence of MWCNTs on copper electrochemical reduction behavior is studied by cathodic polarization and electrochemical impedance spectrums (EIS) analysis. Results show that the existence of the hydrochloric acid purified MWCNTs in the electrolytes shows the accelerating action towards Cu electrochemical reduction during the electrodeposition process, making the Cu films finely grow with the crystal growth toward the (1 1 1) orientation compared to the pure Cu electrodeposited film. The resulting Cu/MWCNT composite film is comprised of Cu matrix and the spatial network of MWCNTs with a considerable high MWCNT content. (C) 2010 Elsevier B.V. All rights reserved.