Glass/indium tin oxide/CdS/CdTe photovoltaic structures were prepared using the high vacuum evaporation method, followed by a typical activation procedure, which involves annealing of the structures at 415–430 °C in the presence of CdCl2 in air.The main purpose of this work was to prepare and evaluate the performance of complete CdS/CdTe solar cell structures with polypyrrole (PPy) back contact and compare it to the structures with standard, copper containing back contact.Back contact layers of PPy doped with ß-naphthalene sulfonate were deposited onto activated CdTe layers by photo-assisted electrodeposition technique in a three-electrode electrochemical cell. It was found that intensive white light illumination from a xenon lamp facilitates PPy deposition at a lower applied potential range and improves quality of obtained polymer films. Applied technique gives the possibility to deposit the PPy layer strictly onto illuminated photoactive CdTe surface eliminating possible short-circuiting through pinholes and cracks in CdTe photoabsorber layer. Furthermore, relatively low deposition potential values give the possibility to reduce electrochemical degradation of CdS/CdTe photovoltaic structure in an electrochemical cell.