A new series of polymers obtained from 3'-alkyl-terthiophene monomers have been electropolymerized aimed at using them as raw materials for the development of electronic devices, e.g., solar cell and organic light-emitting diodes, among others. The polymers were characterized by infrared and UV-Vis spectroscopy and cyclic voltammetry. Cyclic voltammetry results revealed that during polymerization both terthiophene system and substituent groups are oxidized, but these processes are reversible. The products were tested in solar cells and the maximum yield obtained was 0.01%.