The redox reaction between L-ascorbic acid in water and chloranil in nitrobenzene has been studied by means of polarography with an ascending water electrode as well as cyclic voltammetry with a stationary interface. Through accurate measurement of the limiting currents, it has been suggested that the redox reaction should be a two-electron reaction rather than a one-electron reaction described previously. A spectrophotometric technique has also been used to observe that the redox reaction proceeds spontaneously under certain conditions even without electrochemical control. Based on these findings, it has been concluded that the present heterogeneous charge transfer reaction is the ion transfer of chloranil semiquinone radical, which is driven by the homogeneous electron transfer between ascorbic acid and chloranil in the aqueous phase.