The voltammetry of a basal-plane pyrolytic graphite electrode modified with a random ensemble of unsupported microdroplets of vitamin K, is investigated when the electrode is immersed in aqueous electrolytes. It is shown that in dilute acidic solutions, electroreduction occurs in a single two-electron two-proton process to yield the corresponding hydroquinone at the electrode\vitamin K1 microdroplet\aqueous-electrolyte three-phase boundary. On addition of ionic alkali-metal salts to the aqueous acidic phase, the electrochemical reduction of vitamin K1 to the quinol is accompanied by catalytic hydrogen evolution within and alkali-metal-cation insertion into the organic microdroplets. In strongly alkaline solutions, electrochemical reduction of vitamin K1 at the triple-phase junction is proposed as being a single two-electron process with concomitant uptake of alkali-metal cations in order to maintain electroneutrality within the oil phase. Surprisingly, the relative ease of cation insertion into the oil phase is demonstrated to be governed by the degree of ion-pair formation rather than by the Gibbs transfer energy of the cation across the liquid\liquid interface.