However, the inferior energy density of SCs (typically < 5 Wh kg −1) severely restricts their widespread application in large-scale energy storage. [3-5] Based on the evaluation criterion of energy density, the energy density of SCs is proportional to the specific capacity and the square of the operating voltage of the device. [3,6] Therefore, in principle, the key to construct high energy density SCs lies in the electrode material with superb intrinsic characteristics and the electrolyte with high voltage window that is highly matched with the electrode material. To date, many kinds of active materials, such as transition metal hydroxides/oxides, phosphates, and carbon-based materials have been developed as electrode materials for SCs. [7-12] Among them, compounds based on the Faraday reaction tend to possess superior theoretical specific capacity, but due to poor intrinsic conductivity, sluggish kinetics, and collapse-prone structure, the key parameters such as rate capability and cyclability are unsatisfactory. [2,13] As a versatile SCs electrode material, carbon-based materials based on reversible ion adsorption/desorption not only integrate high specific capacity, excellent rate capability, and outstanding cycling performance, but also compatible with various electrolyte systems such as aqueous, organic, and ionic liquid. [14,15] In view of energy storage characteristics, pore structure plays the most vital role in electrochemical properties of carbon-based materials. [16,17] In the inherent cognition, micropores provide active sites to store charge, mesopores contribute channels to promote ion diffusion and transfer, and macropores act as ion buffers. [18,19] However, since the small-sized micropores (d <0.5 nm) are ioninaccessible, as well as the charge storage efficiency of smallsized mesopores (d <4 nm) is comparable to that of micropores, the specific capacity of carbon-based material is not always linearly related to the micropore volume. [2,20-22] Therefore, the active site contributors should be defined as ion-accessible micropores and small-sized mesopores. In view of this, the ideal carbonbased materials for SCs should be a hierarchical porous carbon (HPC), in which the ion-accessible micropores and small-sized mesopores are dominated and supplemented by a reasonable proportion of supermesopores (d >4 nm). The intrinsic properties of carbon-based material and the voltage window of electrolyte are the two key barriers to restrict the energy density of carbonbased supercapacitors (SCs). Herein, a cucurbit[6]uril-derived nitrogen-doped hierarchical porous carbon (CBCx) with unique pore structure characteristics is synthesized and successfully applied to construct SCs based on different electrolyte systems. Owing to narrow pore size distribution (0.5-4 nm), colossal ion-accessible pore volume, prominent supermesopore volume, and reasonable heteroatom configuration, the CBCx-based SCs demonstrate excellent electrochemical performances with high operating voltages in two distinct systems. The optimal SCs...