Three typical anode materials: pure iron (Fe), silicon-rich steel (FeSi) and white cast iron (FeC) electrodes were used in the process of electrochemical ferrate(VI) synthesis in the molten sodium hydroxide. The voltammetric peak current densities corresponding to the first and second step of the anode dissolution in the case of FeC as well as FeSi electrode are higher compared to the pure iron electrode. After passivity region subsequently the transpassive iron dissolution, including ferrate(VI) formation together with an oxygen evolution occurs and the current shoulder is visible for all electrodes used. Measured electrochemical impedance spectra confirm the physical model of the polarized surface based on the concept of two macrohomogeneous surface layers. In all cases the resistance of both inner and outer layer decrease with increasing applied potential. With increasing temperature the resistance of inner and outer layer decreases. The capacity of inner and outer layer increases with increasing potential. This is in agreement with decrease of the resistances of both layers: layers are getting thinner or more disintegrated by oxygen evolution or strong anodic dissolution. The number of exchanged electrons calculated from a static polarization curve at the potentials in ferrate(VI) formation region is z =3 for all electrode materials used.