A binding of ferrocyanide ([Fe(CN) 6 ] 4-) with octa-cationic tetra(viologen) calix [4] resorcine (MVCA 8? ) and its ''model'' compound--dimethyl viologen (MV 2? ) has been studied by cyclic voltammetry in DMSO-H 2 O media (60 vol.% aqueous DMSO, 0.1 M NaClO 4 ). It was found that MV 2? does not interact with ferrocyanide. By contrast, a reversible redox-switchable interaction between [Fe(CN) 6 ] 4-and MVCA 8? has been observed. MVCA 8? forms a 1:1 supramolecular complex MVCA 8? :[Fe(CN) 6 ] 4-with ferrocyanide while its reduced forms (MVCA 4?Á and MVCA 0 ) do not interact with the tetraanion. The switching of the ferrocyanide binding is also observed in the one electron oxidation of [Fe(CN) 6 ] 4-to [Fe(CN) 6 ] 3-. It has been shown, that the calix [4]resorcine in its partial and fully reduced forms and its complex with ferrocyanide form welldefined nanoscale multi-layer films on the electrode surface.