This article demonstrates changes in the structures of poly (3,4-ethylene dioxythiophene): polystyrene sulfonate (PEDOT: PSS) with the addition of organic additives. The mechanisms of PEDOT: PSS are analyzed using X-ray photoelectron spectroscopy (XPS), cross-sectional images obtained from scanning electron microscopy (SEM), and contact angles. In this paper, a bond-breaking reaction and phase separation are successfully found to occur between PEDOT: PSS molecules and the organic additives. Our research also finds that this bond-breaking reaction and phase separation exist in the PEDOT: PSS–sorbitol–maltitol film at the same time. The addition of organic additives will improve the optical properties and the moisture stability of PEDOT: PSS films.