A revised mechanism for the oxidation of the excited state of Ru(bpy)(3)(2+) with the persulfate anion is described in this work. The formation of the precursor complex in the electron transfer reaction involves ion pairing between the metal complex in ground and excited states and S2O82-. The equilibrium constant for the ion-pair formation (K-IP = 2.7 M-1) was determined from electrochemical measurements and analysis of thermal reaction between Ru(bpy)(3)(2+) and persulfate. It was found to be consistent with the calculated value estimated from the Debye-Huckel model. The analysis of rate constants for reactions between persulfate and various metal complexes indicates that thermal and photochemical reactions most likely proceed through a common pathway. Extremely high reorganization energy (ca. 3.54 eV) for the electron transfer obtained from fitting experimental data with the Marcus equation is indicative of significant nuclear reorganization during the electron transfer step. In view of these results the electron transfer can be described as dissociative probably involving substantial elongation or complete scission of the O-O bond. The proposed model accurately describes experimental results for the quenching of *Ru(bpy)(3)(2+) over a wide range of persulfate concentrations and resolves some discrepancies between the values of K-IP and k(et) previously reported. The implications of various factors such as the ionic strength and dielectric constant of the medium are discussed in relation to measurements of the quantum yields in photodriven oxidation reactions employing the Ru(bpy)(3)(2+)/persulfate couple.