The method of electrochemical synthesis of conducting polyphenylacetylene (PPA) layers on Pt, Cu, SnO2 , ITO-surfaces was developed. The influence of electrosynthesis conditions on the structure, morphology, optical spectra and conductivity of PPA films have been studied. The influence of electrosynthesis condition on the electron spectra of PPA films allow to propose the possibility of electrochemical generation in PPA films the free charge carriers by the mechanism of electrochemical doping.