TiO2 porous films were prepared on ITO coated glass slides by the sol-gel dip-coating method assisted with Polyethylene glycol (PEG). The films were used as photo-anodes in the photo-assisted electrolytic removal of cuprous ions in cyanide media. These were characterized by SEM, UV-Visible spectroscopy and XRD. The PEG modified films were free of cracks and developed a porous structure after heat treatment at 500 ºC, due to the thermal decomposition of the structure associated PEG. It was demonstrated that the photo-assisted electrochemical reduction of copper is promoted by the use of modified TiO2 films as photo-anodes, thanks to the greater surface area given by the PEG decomposition. However, the film thickness was found to be a critical factor in the process, to such an extent that films composed of 5 layers were completely inefficient, meaning that despite the open porosity, multilayered films acted as a barrier within the photo-electrolytic process.