The electrochemical response of an electrocatalytic process taking place at a redox mediator modified electrode has been analysed with Square Wave Voltammetry (SWV) and Square Wave Voltcoulometry (SWVC) for which. a simple expression of the current and converted charge have been deduced for the usual experimental situation of high catalytic rate constants. Both techniques give rise to peak-shaped responses whose peak parameters have been deduced in the case of reversible electrochemical step. The influence of key parameters such as the square wave pulse amplitude, the rate constant of the chemical step and the reversibility of the charge transfer has been studied. Moreover, the SWVC charge-potential curves allow an immediate determination of the catalytic rate constant, independently of the value of the electrochemical rate constant. The theoretical predictions have been tested with the electrocatalytic oxidation of ferrocyanide mediated by a mixed 6-(ferrocenyl)hexanethiol-hexanethiol monolayer at a disk gold electrode, and an excellent agreement between theory and experiments has been found. (C) 2009 Elsevier B.V. All rights reserved.