CdTe and CuInSe2 (CIS) thin films were electrodeposited and characterized for photovoltaic applications. Schottky barrier-type photovoltaic junctions were obtained using a heavily doped PMeT (poly-3-methylthiophene), prepared by electropolymerization, displaying nearly metallic behavior, and semiconductors such as CdTe and CIS obtained by electrodeposition. The photovoltaic structures formed and studied are Mo/CIS/PMeT/grid and Mo/CdTe/PMeT/grid Schottky barrier junctions. Solar to electrical conversion efficiency of the order of 1% was obtained in the case of PMeT/CIS and PMeT/CdTe junctions.