Five N-phenylviologen (PV²⁺) derivatives have been synthesized and their electrochemical behavior in the presence of halide anions has been studied. Further investigations were carried out by ¹H and ¹⁹F NMR spectroscopy at different chloride concentrations. This is the first time a systematic study combines cyclic voltammetry and NMR spectroscopy in order to analyse the contribution of halogen bonding among the various non-covalent interactions between iodinated N-phenylviologens. The results show strong evidence for a significant “halogen bonding effect” in the interaction between halides and the iodo-tetrafluoro-phenylviologen PV2+-C6F4I. A significant influence of halogen bonding on reduction potentials of the novel halogen bond donor PV2+-C6F4I has been evidenced resulting in the first example of “inverse redox switching” of an XB-donor being partially deactivated upon reduction. Furthermore the particular binding properties of the perfluorinated derivative PV2+-C6F5 towards chloride are discussed considering a possible contribution of π–anion interaction in solution.