Abstract: Nitrogen doping has been widely used to improve the performance of carbon electrodes in supercapacitors, particularly in terms of their high-frequency response. However, the charge storage and electrolyte ion response mechanisms of different nitrogen dopants at high frequencies are still unclear. In this study, melamine foam carbons with different configurations of surface-doped N were formed by gradient carbonization, and the effects of the configurations on the high-frequency response behavior of the supercapacitors were analyzed. Using a combination of experiments and first-principle calculations, we found that pyrrolic N, characterized by a higher adsorption energy, increases the charge storage capacity of the electrode at high frequencies. On the other hand, graphitic N, with a lower adsorption energy, increases the speed of ion response. We propose the use of adsorption energy as a practical descriptor for electrode/electrolyte design in high-frequency applications, offering a more universal approach for improving the performance of N-doped carbon materials in supercapacitors.