Binder-free self-assembled 3D architecture electrodes have been fabricated by a novel convenient method. Liquid crystalline graphene oxide was used as precursor to interact with poly(3,4-ethylene-dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) in dispersion in order to form a conductive polymer entrapped, self-assembled layer-by-layer structure. This advanced network containing PEDOT:PSS enabled us to ascribe the superior electrochemical properties of particular graphene sheets. This layer-by-layer self-assembled 3D architecture of best performing composite (reduced graphene oxide–PEDOT:PSS 25) showed excellent electrochemical performance of 434 F g−1 through chemical treatment. To highlight these advances, we further explored the practicality of the as-prepared electrode by varying the composite material content. An asymmetric supercapacitor device using aqueous electrolyte was also studied of this same composite. The resulting performance from this set up included a specific capacitance of 132 F g−1. Above all, we observed an increase in specific capacitance (19%) with increase in cycle life emphasizing the excellent stability of this device.