A novel aqueous-based self-assembly approach to a composite of iron oxide nanorods on conductive-polymer (CP)-functionalized, ultralarge graphene oxide (GO) liquid crystals (LCs) is demonstrated here for the fabrication of a flexible hybrid material for charge capacitive application. Uniform decoration of α-Fe2O3 nanorods on a poly(3,4-ethylene-dioxythiophene): poly(styrenesulfonate) (PEDOT:PSS)-functionalized, ultralarge GO scaffold results in a 3D interconnected layer-by-layer (LBL) architecture. This advanced interpenetrating network of ternary components is lightweight, foldable, and possesses highly conductive pathways for facile ion transportation and charge storage, making it promising for high-performance energy-storage applications. Having such structural merits and good synergistic effects, the flexible architecture exhibits a high specific discharge capacitance of 875 F g-1 and excellent volumetric specific capacitance of 868 F cm-3 at 5 mV s-1, as well as a promising energy density of 118 W h kg-1 (at 0.5 A g-1) and promising cyclability, with capacity retention of 100% after 5000 charge-discharge (CD) cycles. This synthesis method provides a simple, yet efficient approach for the solution-processed LBL insertion of the hematite nanorods (HNR) into CP-functionalized novel composite structure. It provides great promise for the fabrication of a variety of metal-oxide (MO)-nanomaterial-based binder and current collector-free flexible composite electrodes for high-performance energy-storage applications. A liquid-crystalline novel self-assembly approach is used to develop a flexible material for charge capacitive applications. Highly porous hematite (α-Fe2O3) nanorods (HNRs) prepared by an advanced spray-precipitation method enable the fabrication with ultralarge graphene oxide (GO) functionalized by PEDOT:PSS in an aqueous medium to develop a novel self-assembled 3D architecture with excellent energy-storage performance.