Poly(paraphenylene vinylene) was prepared by electrochemical reduction of alpha,alpha,alpha＇,alpha＇-tetrabromo-p-xylene. The effect of different parameters on the quality of the formed polymer film was studied: monomer material, supporting electrolyte, electrode material, polymerization potential and the preparation procedure. The films polymerized in different electrolyte solutions were studied by sweep electron microscopy (SEM), cyclic voltammetry (CV) and with in situ conductometry measurements. Energy dispersive X-ray analysis (EDXA), dispersive Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy techniques were used to study the structure of the formed polymer films.