In addition, ion desolvation/dehydration plays a pivotal role in the charging dynamics of subnanometer pores. Understanding the intricate relationships among ion pairing, ion desolvation, and the resulting EDL structure is essential for designing high-performance electrochemical capacitors with water-in-salt electrolytes. In-situ techniques such as NMR, EQCM, and EQCA are commonly used to investigate desolvation in diluted electrolytes. However, to the best of our knowledge, ion desolvation in water-in-salt electrolytes within carbon pores has not been systematically studied yet. Furthermore, carbon electrodes often possess a complex architecture with sub-nanometer micro-, meso-, and macropores, which results in sluggish ion transport of water-in-salt electrolyte. Additionally, these sub-nanopores present significant challenges for utilizing those mentioned experimental techniques and models to effectively determine and differentiate ion desolvation and the resulting EDL structures within different pores of a multiporous frameworks.