The electron transfer across the liquid|liquid interface between aqueous solutions (W) of FeIII/II compounds (hexacyanoferrates, chlorides) and a (t-butyl) substituted LuIIIbisphthalocyanine in dichlorohexane (DCH) or nitrobenzene (NB), has been studied by voltammetry at a microinterface and by spectrophotometry. The electron transfer wave has been observed only at the W|DCH. Coupling with an ion transfer facilitates this electron transfer: the LuIIIbisphthalocyanine has been oxidized or reduced across the W|NB interface, depending on the ion establishing the interfacial potential.