From the anodic peak currents of cyclic voltammograms for Ag(I)/Ag(II) couple obtained with the variation of nitric acid concentration, Ag(I) concentration and solution temperature at a Pt electrode in concentrated nitric acid solutions, the diffusion coefficients of Ag(I) ion were evaluated to estimate the limiting current density of Ag(II)-mediated electrochemical oxidation (MEO) process, which has been effectively used for the complete destruction of hazardous organic materials. The results showed that, due to the water decomposition reaction which occurred simultaneously with the Ag(I) ion oxidation, background subtractions for the cyclic voltammograms were required to estimate the correct peak currents. The empirical relationship for the diffusion coefficient of Ag(I) was suggested as a function of solution viscosity and temperature.