Electrostatic discharge (ESD) protection is quite necessary for the electronic industry and modern life. Antistatic materials based on poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) have been widely used in these fields such as electronic devices, smart windows, specialty papers, photographic films, glass coatings, fabrics and so on. To solve the critical shortcomings of PEDOT:PSS in high commercial price, high water absorption accompanying dramatically decreased structure stability, mechanical damage vulnerability, and insufficient substrate adhesion ability, etc., herein, we prepared an antistatic PEDOT:PSS/Epoxy films from self-made PEDOT:PSS aqueous dispersion and waterborne epoxy system by facile mechanical mixing and drop-casting on glass substrates. The surface morphology, volume resistivity, surface wettability and water immersion stability of these films were systematically studied. In addition, the substrate adhesion and surface hardness of the films after the introduction of polyhedral oligomeric silsesquioxane (POSS) and silane coupling agent (SCA) in such composite systems were investigated. The optimized PEDOT:PSS/Epoxy/POSS/SCA films exhibited fine antistatic ability, increased hydrophobicity, improved water stability, high hardness (HB) and good adhesion (level 1) on glass substrates. Such conductive films together with their design principle and their environmentally friendly waterborne mother dispersions will promote the further use of PEDOT:PSS in ESD protection materials or others in organic film electronics including vigorously developed flexible and wearable electronic devices.