Onsager's formalism of nonequilibrium Thermodynamics is employed to analyze competitive diffusion processes pertaining to charge transport through redox polymer electrodes. The validity of reciprocity relations is demonstrated for electron hopping in the case of [RU(NH3)(6)](3+/2+) couple on Nafion coated Glassy Carbon (GC) electrodes. The phenomenological coefficients pertaining to electron hopping and physical diffusion are estimated using the experimental data of Cp(2)FeTMA(2+/1+) on Nafion coated GC electrodes. The redox conductivity and transport numbers are expressed in terms of Onsager's coefficients and the calculation of the phenomenological coefficients directly from the charge propagation behavior is demonstrated. The expression for entropy production is shown to yield new insights regarding the interpretation of diffusion coefficients in redox polymeric systems.