Here we propose the use of solid-state nuclear magnetic resonance (NMR) spectroscopy to reveal ion electrosorption in a layered MOF. NMR has been demonstrated to be a powerful technique to probe and quantify the electrolyte environments in porous carbon electrodes. In these materials, 'in-pore' and 'ex-pore' electrolyte environments can be identified from NMR spectra, where the chemical shift dependence of the in-pore resonances are dominated by ring current effects. This leads to a characteristic nucleus independent chemical shift (NICS) of the in-pore environment which is shielded significantly relative to the neat electrolyte. Utilising this assignment, charging mechanisms of porous carbon supercapacitors have been studied by measuring how the in-pore ion populations change upon charging through both ex-situ and in-situ NMR experiments. In contrast to EQCM and SANS, NMR can selectively and quantitatively probe cations, anions and solvent species in the system by observing different nuclei and therefore has the potential to resolve some of the existing ambiguity in the literature on MOF electrodes. Indeed, NMR has already been used to identify and quantify 'in-pore' molecular environments in non-conductive MOFs, where the in-pore chemical shift has been found to arise from a competing combination of coordination, solvation and ring-current effects. NMR relaxometry has similarly demonstrated the potential to identify guest species in paramagnetic MOFs, as well as probing material porosities, providing several potential useful applications for NMR to be explored on porous conductive MOFs for electrochemical applications. Despite this, the application of NMR to study adsorption behaviour of conductive layered MOFs remains unreported.