Conductive layered metal-organic frameworks (MOFs) are a class of crystalline materials, that feature high intrinsic porosities and conductivities. These properties have led to promising applications across a diverse range of research fields including energy storage, electrochemical sensing, electrocatalysis, thermoelectrics and spintronics. In particular, conductive MOFs of high porosity make ideal electrodes for energy storage in supercapacitors. The tuneable structure of these materials, achieved through varying the identity of the constituent metal ions and organic linkers, presents an exciting opportunity for understanding molecular-level electrolyte-electrode interactions, and how these interactions impact electrochemical performance. This understanding will be essential for systematic optimisation of electrochemical systems and to overcome the various challenges facing MOF-based supercapacitors, such as their limited charging rates compared to conventional activated carbon-based supercapacitors. Initial theoretical and experimental studies have begun to investigate the electrochemical interface of conductive layered metal-organic frameworks and to study charge storage in conductive MOFs. Bi et al., used molecular dynamics (MD) simulations to study the charge storage mechanism in MOFs with various pore sizes, including Ni3(HITP)2, with an ionic liquid electrolyte. This study offered the first insights into the ion distribution at the electrochemical interface for MOFs, revealing distinct distributions of in-pore cations and anions. Further computational studies have built on these foundations by using a hybrid quantum-mechanics/molecular-mechanics (QM/MM) approach to study the interface of the related layered MOF, copper 2,3,6,7,10,11-hexahydroxytriphenylene, Cu3(HHTP)2, with the benchmark organic electrolyte tetraethylammonium tetrafluoroborate in acetonitrile (NEt4BF4/ACN). This latter approach more accurately revealed the charge density distribution at the electric double-layer interface, and was used to assess the favourability of different charging mechanisms for the system. The study suggested that predicted capacitance values for cation-dominated charging mechanisms matched most closely with experimental measurements for this system, and that the preferred anion sorption sites were dependent on the electrode polarity.