To conclude, high molecular weight PEDOTs were photochemically synthesized using PAB as a single-component photoinitiator. This new method has several advantages; the irradiation wavelength can be switched depending on the PAB concentration, bulk photopolymerization is possible due to the solubility of PAB in EDOT, in high concentrations of PAB the photopolymerization reaction is very fast (supplementary video 2), PEDOT formed has high molecular weight and high conductivity. Moreover, the photopolymerization can be performed under mild reaction conditions (room temperature, air atmosphere, ethanol solvent/bulk). OPV applications of the high molecular weight PEDOT are ongoing.