The cobalt hexacyanoferrate, MhCokA[Fe-B(CN)(6)](t), (where M is an alkali metal cation, and the subscripts h, k, and l are stoichiometric coefficients, and A and B are the formal oxidation states of the Co and Fe metal sites in the structure) was shown to contain a rich series of compounds that are inter-linked through various redox processes (involving both electron and cation transfer) either in the dark or under the near-infrared (IR) activation. These processes were studied by a combined use of cyclic voltammetry, in situ IR spectroelectrochemistry (using both intensity or potential modulation), and ex situ X-ray photoelectron spectroscopy.