Fourier transform large amplitude alternating current voltammetry (FTACV) studies are reported on an electrocatalytic (EC') mechanistic system which exhibits split wave behavior on both macro- and micro-size working electrodes. The electrochemical characteristics of the EC' mechanism were analysed using the fundamental to fourth harmonic components deduced by the Fourier transform algorithm. The effects of the sinusoidal frequencies of the applied potential, electrode geometry and substrate concentrations are investigated. The split wave phenomenon was observed and explored particularly.