The conversion process of “insoluble” prussian blue (PB) films into the “soluble” structure has been followed by the simultaneous measurement of current and mass changes during voltammetric experiments and focusing on the possibilities of the use of the instantaneous mass/electrical charge ratio at each potential. A similar procedure was used for the analysis of the mechanism of reduction of PB films to the Everitt’s salt form and to follow the partial dissolution of iron species during the oxidation to the prussian yellow form. The possibility of covering PB films by Nafion membranes, which make difficult the transport of anions through it, allows us to discern the role of anions in the solubilization process of PB films.