Graphene oxide (GO)-doped dimethyl sulfate (DMS)/poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) superconductive alignment layer, aligning liquid crystals (LCs) with super switching and non-residual direct current (non-residual DC) performance, is presented in this manuscript. Doping of GO increased the pristine polar energy of a thin composite layer as well as the corresponding anchoring energy of the LCs sandwiched between these thin layers but only slightly affected the thin layers' morphology. When rubbed GO/DMS/PEDOT:PSS composite layers were used as alignment layers, a homogeneous alignment of nematic LCs was observed with competitive optoelectrical switching properties and non-residual DC performance because of the enhanced field effect and charge transport induced by the doped GO.