Biomass-derived carbonaceous materials have been deemed to be one of the up-and-coming electrode materials for high-performance energy storage systems due to their cost-neutral abundant resources, sustainable nature, easy synthesis methods, and environmentally benign features. In this work, various graphene-like porous carbon networks (GPCs) with three-dimensional (3D) hierarchically ordered “ion highways” have been synthesized by the carbonization/activation of orange-peel wastes for use as an electrode material in high-energy supercapacitors. The porous structures and surface morphologies of the GPCs were rationally fine-tuned as a function of the activation agent ratio. The prepared GPCs offered superior specific surface area in addition to a 3D porous structure with a fine-tuned pore size distribution. The electrochemical behaviors of all the GPCs were evaluated in 6.0 M KOH aqueous electrolyte via a three-electrode electrochemical setup. Owing to their synergistic characteristics, including superior specific surface area (1150 m² g⁻¹), large pore volume, and fine-tuned 3D porous architecture, GPC-3.0 (synthesized with a KOH : GPC ratio of 3.0, by wt.) exhibited the best capacitive behavior amongst the studied GPCs. The 3D hierarchically ordered architecture acts like well-designed ion highways that boost electron transportation, thereby enhancing electrochemical energy storage. A coin-cell-type symmetrical supercapacitor based on GPC-3.0 was tested in both 1.0 M Na₂SO₄ (salt-in-water) and 12.0 m NaNO₃ (water-in-salt) electrolytes. The supercapacitor cell based on the water-in-salt electrolyte offered a wide operating voltage of 2.3 V. The obtained energy density and power density values were comparable to those of commercial high-performance electrical double-layer capacitors. Such notable findings will shed light on next-generation high-rate electrochemical energy storage systems based on biomass-derived carbonaceous materials.