The solution-phase voltammetry of the modular podand, 1,3,5-tris(3-((ferrocenylmethyl)amino)pyridiniumyl)-2,4,6-triethylbenzene hexafluorophosphate, [PD] [PF6](3), in acetonitrile (0. 1 M Bu4NPF6) and the ionic liquids [1-butyl-3-methylimidazolium hexafluorophosphate, (ethylmethylimidazoliumyl)bis(trifluoromethylsulfonyl)-amide, and (n-butylmethylpyrrolidiniumyl)bis(trifluoromethylsulfonyl)amide] exhibits a well-defined diffusion-controlled process at a potential of about 1.40 V vs [Co(eta(5)-C5H5)(2)](+/0). Detailed chrorroamperometric and near steady-state microdisk electrode studies reveal that although the process has many of the characteristics of a reversible one-electron oxidation reaction, it is actually a combination of three very closely spaced reversible one-electron processes, implying that there is minimal communication between the three ferrocenyl redox active centers present in the podand. The voltammetry of very slowly dissolving microparticles of [PD][PF6](3) mechanically attached to an electrode surface in contact with ionic liquids is indistinguishable from that observed when the podand is in the dissolved state in the ionic liquid. In contrast, cyclic voltammograms obtained when a [PD][PF6](3) modified electrode is in contact with aqueous electrolyte media exhibit behavior very different from that found in the solution phase. For example, in the presence of KPF6 electrolyte, three resolved oxidation peaks are detected, whereas in some other electrolyte media, transformations to features expected in stripping voltammetry are encountered on repetitive cycling of the potential. Unlike the case in ionic liquids, [PD][PF6](3) is thermodynarttically insoluble in water, although oxidized forms are believed to have an anion dependent level of solubility. Consequently, an oxidation-dissolution/reduction-reprecipitation and ion exchange type mechanism is believed to lead to a transition from the "thick" to "thin" film type of voltammetric behavior, which is supported by numerical simulation.