High conductivity, good stability, and high transmittance in the visible region are the three essential requirements for the polymer electrodes used in the optoelectronic devices. It was found that with addition of diols, such as ethylene glycol, diethylene glycol, or poly(ethylene glycol) (PEG), to the poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT:PSS) emulsion before spin-coating could increase dramatically the conductivities of the resultant PEDOT:PSS thin films from 1 to 90 S cm(-1) while maintain the optical transparency of the modified thin films. With up to -2.4 V potential applied, the PEDOT:PSS with PEG 200 additive does not show obvious color change, indicating its good electrochemical stability as polymer electrode. Detailed studies on the structures and morphologies of these modified PEDOT:PSS thin films, in comparison to that of PEDOT:PSS without additives were carried out using AFM, Raman, and FTIR to investigate the underlying mechanisms.