The work aims to synthesize a high-performance and environmental-friendly polymeric materials in aqueous solutions. Three kinds of doped PEDOT:PSS (PEDOT:PSS/DES) were electrochemically polymerized in aqueous solutions containing sodium polystyrene sulfonate (PSS) and deep eutectic solvents (DES) dopants with 3,4-ethylenedioxythiophene (EDOT) as monomer in three-electrode system. The molecular structure characteristics of the as-prepared polymers were analyzed by Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS), while the optical properties of the film were studied by ultraviolet-visible spectroscopy (UV-Vis). The research results indicated that DES prompted the blueshift of the peak associated with π-π transition and the improvement of conjugate degree. Correspondingly, the maximum absorption value contrast was increased at 0.30 or above from 0.27. In conclusion, DES doping is helpful to improve the molecular conjugate degree and photoelectric conversion characteristics of films and provide strong support for the design and application of new optoelectronic devices.