AbstractUnderstanding how water interacts with nanopores of carbonaceous electrodes is crucial for energy storage and conversion applications. A high surface area of carbonaceous materials does not necessarily need to translate to a high electrolyte‐solid interface area. Herein, we study the interaction of water with nanoporous C1N1 materials to explain their very low specific capacitance in aqueous electrolytes despite their high surface area. Water was used to probe chemical environments, provided by pores of different sizes, in 1H MAS NMR experiments. We observe that regardless of their high hydrophilicity, only a negligible portion of water can enter the nanopores of C1N1, in contrast to a reference pure carbon material with a similar pore structure. The common paradigm that water easily enters hydrophilic pores does not apply to C1N1 nanopores below a few nanometers. Calorimetric and sorption experiments demonstrated strong water adsorption on the C1N1 surface, which restricts water mobility across the interface and impedes its penetration into the nanopores.