The transfer of F^- ion assisted by an organometallic complex cation tetraphenylantimony (TPhSb⁺) across the polarized nitrobenzene | water (NB | W) interface has been studied by means of ion-transfer voltammetry. A well-defined voltammetric wave was observed within the potential window at the NB | W interface when tetraphenylantimony tetrakis(4-chlorophenyl) borate and F^- ion were present in NB and W, respectively. The voltammogram can be interpreted as being due to the reversible transfer of F^- ion assisted by the formation of the TPhSbF complex through the coordination of F^- to Sb atom in NB. The formal formation constant of TPhSbF in NB has been determined to be 10^10.95±0.2 M^-1. No voltammetric wave due to the TPhSb⁺-assisted transfer of other anions such as Cl^-, Br^-, I^-, NO₃^-, CH₃COO^- and H₂PO₄^- ions has been observed within the potential window.