Recently, with the development of personal wearable electronic devices, the demand for portable power is miniaturization and flexibility. Electro-conductive hydrogels (ECHs) are considered to have great application prospects in portable energy-storage devices. However, the synergistic properties of self-healability, viscoelasticity, and ideal electrochemistry are key problems. Herein, a novel ECH was synthesized by combining polyvinyl alcohol-borax (PVA) hydrogel matrix and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-cellulose nanofibers (TOCNFs), carbon nanotubes (CNTs), and polyaniline (PANI). Among them, CNTs provided excellent electrical conductivity; TOCNFs acted as a dispersant to help CNTs form a stable suspension; PANI enhanced electrochemical performance by forming a “core-shell” structural composite. The freeze-standing composite hydrogel with a hierarchical 3D-network structure possessed the compression stress (~152 kPa) and storage modulus (~18.2 kPa). The composite hydrogel also possessed low density (~1.2 g cm⁻³), high water-content (~95%), excellent flexibility, self-healing capability, electrical conductivity (15.3 S m⁻¹), and specific capacitance of 226.8 F g⁻¹ at 0.4 A g⁻¹. The fabricated solid-state all-in-one supercapacitor device remained capacitance retention (~90%) after 10 cutting/healing cycles and capacitance retention (~85%) after 1000 bending cycles. The novel ECH had potential applications in advanced personalized wearable electronic devices.