The kinetics of the electron transfer between NADH and ferrocenecarboxylic acid (FMCA) catalyzed by diaphorase from Clostridium kluveri (EC 1.8.1.4.) was studied by voltammetry. A commercially available digital simulation program permitted one to determine the rate constants of the catalytic system by a ®tting procedure. A rate constant of 3610 4 M À1 s À1 was found for the reaction between diaphorase and mediator while a value of 8 M À1 s À1 was found for the parallel competitive reaction between NADH and mediator. In addition a comparison of the present method to other data treatment procedures reported in the literature and a brief evaluation of their limits of applicability were carried out.