The electrochemistry of the water oxidation catalyst, Rb(8)K(2)[ Ru(4)O(4)(OH)(2)(H(2)O)(4) (gamma-SiW(10)O(36))(2)] (Rb(8)K(2)-1(0)) has been studied in the presence and absence of potassium cations in both hydrochloric and sulfuric acid solutions by transient direct current (dc) cyclic voltammetry, a steady state dc method in the rotating disk configuration and the kinetically sensitive technique of Fourier transformed large-amplitude alternating current (ac) voltammetry. In acidic media, the presence of potassium ions affects the kinetics (apparent rate of electron transfer) and thermodynamics (reversible potentials) of the eight processes (A /A to H/H ) that are readily detected under dc voltammetric conditions. The six most positive processes (A /A to F/F ), each involve a one electron ruthenium based charge transfer step (A /A, B /B are Ru(IV/V) oxidation and C/C to F/F are Ru(IV/III) reduction). The apparent rate of electron transfer of the ruthenium centers in sulfuric acid is higher than in hydrochloric acid. The addition of potassium cations increases the apparent rates and gives rise to a small shift of reversible potential. Simulations of the Fourier transformed ac voltammetry method show that the B /B, E/E , and F/F processes are quasi-reversible, while the others are close to reversible. A third Ru(IV/V) oxidation process is observed just prior to the positive potential limit via dc methods. Importantly, the ability of the higher harmonic components of the ac method to discriminate against the irreversible background solvent process allows this (process I) as well as an additional fourth reversible ruthenium based process (J) to be readily identified. The steady-state rotating disk electrode (RDE) method confirmed that all four Ru-centers in Rb(8)K(2)-1(0) are in oxidation state IV. The dc and ac data indicate that reversible potentials of the four ruthenium centers are evenly spaced, which may be relevant to understanding of the water oxidation electrocatalysis. A profound effect of the potassium cation is observed for the one-electron transfer process (G/G ) assigned to Ru(III/II) reduction and the multiple electron transfer reduction process (H/H ) that arise from the tungstate polyoxometalate framework. A significant shift of EA? to a more positive potential value for process H/H was observed on removal of K(+) (100 mV in H(2)SO(4) and 50 mV in HCl).