An error analysis of the potential and voltage step relaxation techniques is presented. For this error analysis, applicability of six data‐evaluation methods, ranging from simple graphical analysis to computer curve fitting, is investigated. The results are presented in applicability diagrams in terms of three characteristic times of the electrode reaction: , the time constant of the double layer capacitance—reaction resistance system; , the time constant of the diffusion impedance—reaction resistance system; and , the time constant of the double layer capacitance—solution resistance system. The error analysis takes into consideration (i) all random errors caused by the measurement of potential, solution resistance, and current density relaxation, and (ii) systematic errors caused by the mathematical approximations used in the data‐evaluation methods, the neglect of the finite rise time of the potentiostat, and the neglect of the effect of the uncompensated solution resistance. It is shown that a computer curve‐fitting data‐evaluation method, which eliminates the systematic errors, can extend the field of applicability to reactions at least five times faster than those measurable with the simplest graphical method, and, under the best conditions, the field can be extended to reactions faster by as much as two orders of magnitude. Under identical conditions, the limitations of the voltage step technique are the same as those of the potential step technique, but the practically achievable values will usually be larger for the voltage step technique and, consequently, the field of applicability will be decreased.