A new molecular Br-2-catalyzed polymerization of 2,5-dibromo-3,4,ethylenedioicyselenophene (DBEDOS), 2,5-rdibromo-3,4-ethylenedioxythiophene (DEEDOT), and their analogues, providing metal free and virtually defect free conducting polymers under mild reaction conditions. The resulting poly(3,4-ethylenedioxyserenophene) (PEDOS), poly(3,4-ethylenedipxythiophene) (PEDOT) and their analogues are electroactive, highly conducting and shown optoelectronic properties practically identical to electrochemically prepared insoluble thin films. This polymerization is a rare example of metal free polymerization which lead to the formation of conjugated polymer. Details characterizations of the obtained polymers were carried out and spectra electrochemistry of PEDOS-C-12 film obtained by Br-2-catalyzed polymerization suggest higher Conductivity and trarisparency coil-Tared to -PEDOS-C-12 film obtained by other methods.