A single-step method for the preparation of thin sol-gel/copper mixed films is described, which is based on a novel electrochemical sol-gel methodology, resulting in nanocomposite coating. The method combines electrochemistry with the acceleration of sol-gel hydrolysis and condensation processes. While sol-gel is deposited as a result of increasing the pH in the vicinity of the electrode surface, copper ions are electrochemically reduced. Characterization of the deposited films was accomplished by scanning electron microscopy, X-ray photoelectron spectroscopy, tunneling atomic force microscopy, and other surface techniques. The different parameters that affect the structure and composition of the deposited films have been examined. We found that the morphology and grain size of the films are strongly affected by the ratio between the sol-gel monomer and copper ions. Furthermore, the potential of deposition affects also the composition of the films as it controls the kinetics of sol-gel and copper deposition.