In this work, high transmittance vertical alignment (VA) liquid crystal (LC) cells were accomplished by using highly conductive PEDOT:PSS films and polyhedral oligomeric silsesquioxane (POSS) nanoparticles. PEDOT:PSS films could be used as the transparent electrode and treated with rubbing process. Therefore, high contrast ratio VA cell without disclination lines could be achieved. Moreover, the electro-optical properties of LC cells fabricated by the rubbed PEDOT:PSS films and POSS were comparable to those constructed by indium tin oxide (ITO) and polyimide. Our work shows the potential of POSS-induced VA on rubbed PEDOT:PSS films for ITO-free and flexible LC displays.