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The triple phase boundary transfer of anions from the aqueous into an organic phase can be driven electrochemically here with the tetraphenylporphyrinato-Mn(III/II) (or TPPMn) redox system in 4-(3-phenylpropyl)-pyridine) (or PPP). Anions investigated are perchlorate, chloride, fluoride, and bicarbonate. The bicarbonate and fluoride transfer processes are shown to be chemically more complex compared to the perchlorate and chloride cases with UV-vis-spectroelectrochemical measurements indicating a combination of HCO3-/CO32- transfer processes and association of fluoride with TPPMn(III)+, respectively. In situ spectroelectrochemistry is developed for ion-transfer voltammetry into sub-microliter organic phase regions on mesoporous ITO conducting film electrodes.