AbstractDrawbacks of the well‐known potential‐step method are briefly mentioned. A new method called the cyclic potential‐step method is introduced, the essential of which is that a square wave voltage is applied to a polarisable electrode. It is shown mathematically that the current response approaches rapidly to a constant pattern. The derivations presented are free from restrictions concerning the reversibility of the system and the magnitude of the amplitude of the square wave.It is shown that the cyclic potential‐step method offers easy means for the determination of the transfer‐coefficient (α) and the standard exchange current density (j00).