A droplet of aqueous solution containing a certain molar ratio of redox couple is first attached onto a platinum electrode surface, then the resulting drop electrode is immersed into the organic solution containing very hydrophobic electrolyte. Combined with reference and counter electrodes, a classical three-electrode system has been constructed. Ion transfer (IT) and electron transfer (ET) are investigated systematically using three-electrode voltammetry. Potassium ion transfer and electron transfer between potassium ferricyanide in the aqueous phase and ferrocene in nitrobenzene are observed with potassium ferricyanide/potassium ferrocyanide as the redox couple. Meanwhile, the transfer reactions of lithium, sodium, potassium, proton and ammonium ions are obtained with ferric sulfate/ferrous sulfate as the redox couple. The formal transfer potentials and the standard Gibbs transfer energy of these ions are evaluated and consistent with the results obtained by a four-electrode system and other methods. A droplet of aqueous solution containing a certain molar ratio of redox couple is first certain attached to a platinum electrode surface, then the resulting drop electrode is immersed into organic solution containing very hydrophobic electrolyte. system has been constructed. Ion transfer (IT) and electron transfer (ET) are been systematically using three-electrode voltammetry. Potassium ion transfer and electron transfer between potassium ferricyanide in the aqueous phase and ferrocene in nitrobenzene are observed with potassium ferricyanide / potassium ferrocyanide as the redox couple. Meanwhile, the transfer reactions of lithium, sodium, potassium, proton and ammonium ions are obtained with ferric sulfate / ferrous sulfate as the redox couple. The formal transfer potentials and the standard Gibbs transfer energy of these ions are evaluated and consistent with the results obtained by a four-electrode system and other methods.