In summary, the significance of this work lies in the fact that it provides a promising complementary strategy for selecting nanoporous carbon materials. BET analysis and pore-size distribution remain useful for pore characterization, but they do not describe either the local structure of the carbon wall or the fraction of that structure reached by the working electrolyte. The study establishes a measurable relations hip among local domain size, electrolyte-ion accessibility, and capacitance, while also showing that no single descriptor is sufficient. This study not only emphasizes the importance of disordered structures, but also indicates that by using NMR technology, we can simultaneously quantify the degree of disorder and the ion accessibility, and thereby predict the capacitance value. This shifts the focus of design from optimization centered on porosity to a design approach guided by the degree of disorder and ionic accessibility. Although highly disordered carbon materials with extremely high porosity can offer excellent gravitational capacitance performance, they may simultaneously reduce electrode density, volumetric capacitance, conductivity, and stability. Therefore, the design of nanoporous carbon materials should balance mass performance, volumetric performance, conductivity, and stability, rather than simply maximizing surface area.