Here, we report, the first photoinduced step-growth polymerization of EDOT using 2bromoacetopheneone (phenacyl bromide (PAB)) as a cheap, single-component photoinitiator under near-UV, visible and daylight. Best to our knowledge, this is also the first study reporting the synthesis of PEDOT using a single-component photoinitating system. Depending on the concentration of PAB, the irradiation wavelength can be tuned from UV to visible region. Besides the probability of using ethanol (EtOH) as a green reaction solvent, bulk photopolymerization was also successful due to the high solubility of PAB in EDOT. Conductivity measurements were also employed to check the conductivity of the doped and dedoped PEDOTs. Doped PEDOT was thoroughly characterized using different spectral and chromatographic methods including UV-Vis, fluorescence, infrared, nuclear magnetic resonance (NMR) spectroscopies and gel-permeation chromatography (GPC). Thermal stability and crystallinity of both polymers were also investigated using thermogravimetric analysis (TGA) and powder X-ray diffractometry (PXRD), respectively. Finally, the redox potential was measured to calculate the electronic band gap of doped PEDOT. Experimental details and the instrumentation can be found in the supporting information.