The depletion of Li resources, their production and end-of-life environmental concerns, and the chance of thermal runaway for Li-ion batteries all necessitate the discovery of alternative, high energy density battery technologies for electronics and transportation. Inorganic frameworks such as Prussian Blue analogs are promising cathode and anode materials for batteries due to their multi-redox center tunability, structural and electrochemical stability, ionic conductivity, and ease of synthesis. Employing the multivalency and higher stability of divalent and trivalent cations and the high ionic conductivity of ionic liquids could improve electrode stability and energy densities. Fundamentally, these studies provide more detailed understanding of the kinetics and mechanisms of intercalation in inorganic frameworks as a function of lattice parameters, ionic radii, and ion solvation while also probing the solid-electrolyte interface between inorganic frameworks and ionic liquids. Our group emphasizes “operando” characterization of these electrodes using XAS and other spectroscopic techniques.