A simple methodology for kinetic measurements of electrode processes is proposed under conditions of square-wave voltammetry (swv) at a constant scan rate of the voltammetric experiment. The method requires measurement of the peak potential separation between the forward and backward components of the voltammetric response by varying the sw amplitude, i.e., the height of the potential pulses. The methodology is equally valid for electrode reactions of an immobilized and dissolved redox couple. The estimation of the standard rate constant can be carried out either by direct fitting between the simulated and experimentally measured data, or by using the working curves derived by simulations. The proposed methodology was confirmed by kinetic measurements of the electrode reactions of azobenzene, immobilized on mercury electrode, and dissolved hexacyanoferrate at glassy carbon electrode. (C) 2013 Elsevier Ltd. All rights reserved.