We describe the electrochemical behavior of solid copper hexacyanoferrate (powder) investigated in the absence of contact with a liquid external supporting electrolyte. In addition to a typical hexacyanoferrate(III,II) redox transition, the system is characterized by a second electrode process which appears at more negative potentials. Diagnostic experiments, which include spectrochemical and solid-state voltammetric characterization, support our view that the latter redox reaction most likely originates from reduction of the system's lattice copper(II) ions. The overall dynamics of charge transport in the material, when discussed in terms of effective diffusion, is moderately high (on the level of 10−8 cm2 s−1). Comparison has been also made to the electrochemical behavior of solid Prussian blue and to the voltammetric characteristics of conventional electrodes modified with thin films of copper hexacyanoferrate.