The green synthesis strategy for cellulose-containing hydrogel electrolytes is significant for effectively managing resources, energy, and environmental concerns in the contemporary world. Herein, we propose an all-green strategy using AlCl3/ZnCl2/H2O solvent to create cellulose/polyacrylamide-based hydrogel (AZ-Cel/PAM) with expanded hierarchical topologies. The aqueous AlCl3/ZnCl2 facilitates the efficient dissolution of cellulose at room temperature, and the dispersed Al3+-Zn2+ ions autocatalytic system catalyzes in-situ polymerization of acrylamide (AM) monomer. This expands the AM network within the cellulose framework, forming multiple bonding interactions and stable ion channels. The resulting hybrid hydrogel exhibits improved mechanical properties (tensile strength of 56.54kPa and compressive strength of 359.43kPa) and enhanced ionic conductivity (1.99 S/m). Furthermore, it also demonstrates excellent adhesion, freeze resistance (-45°C), and water retention capabilities. Quantum simulations further clarify the mechanical composition and ion transport mechanism of AZ-Cel/PAM hydrogels. The assembled supercapacitor with the hydrogel electrolyte, demonstrates an ideal area-specific capacitance of 203.80 mF/cm2. This all-green strategy presents a novel approach to developing sustainable energy storage devices.