New methods for analysis of current‐potential curves in terms of their derivatives are suggested for studies of heterogeneous electron‐transfer reactions. Consequences of the Butler‐Volmer theory on the shape of the derivatives are illustrated. Comparisons are made between fast and slow electron‐transfer reactions for various values of the standard heterogeneous rate constants false(k0false) and the transfer coefficient (α) utilizing asymmetries found in the peak shapes of the derivatives from a dc polarogram. Various parameters which characterize the peak asymmetry (such as ratios of peak‐currents and ratios of peak‐widths) are evaluated and analyzed. They are symmetrical for a reversible process, while they become asymmetrical for slower heterogeneous kinetic systems. It is shown that α for irreversible processes can be directly determined from measurements of peak‐widths or peak‐separations of derivatives. Simultaneous determination of the heterogeneous kinetic parameters ( k0 and α) for several systems is accomplished by fitting the theoretical derivative equation to the experimental data which are obtained with a moving‐window‐smoothing/differentiation method. The results agree well with those obtained with other methods such as dc, ac, semi‐integral, differential pulse polarography, and square‐wave voltammetry.