The aromatic-unit, commercially available, and cost-effective precursor 3, 4-ethylenedioxythiophene (EDOT), was employed instead of bis-EDOT to generate by in-situ photoelectrochemical polymerization (PEP) a conducting polymer-type hole conductor poly (3, 4-ethylenedioxythiophene) (PEDOT) for dye sensitized solar cell (DSC) devices. In order to conduct efficiently the PEP of EDOT, two electrolytic media, aqueous micellar and organic, and two Donor-π-Acceptor sensitizers, were investigated. By using the electrolytic aqueous micellar medium, the PEP was efficient due to the low oxidation potential of the precursor in water. A DSC device based on PEDOT generated from aqueous PEP showed an energy conversion efficiency (η) of 3.0% under 100 mWcm−2, higher by two orders of magnitude than that of a DSC device based on PEDOT from organic PEP (η = 0.04%). The comparison of the properties of the as-obtained PEDOT polymers from aqueous and organic PEP by UV-VIS-NIR measurements shows the formation of PEDOT at a highly doped state from aqueous PEP. The thermodynamic and kinetic requirements for efficiency of PEP process in each medium are investigated and discussed on the basis of the light absorption abilities and electrochemical redox potentials measured for the two organic sensitizers.