Transient and stationary electrochemical behaviours for a first-order catalytic process have been analysed in order to show that a true stationary response only depends on the homogeneous rate constant values is obtained, in contrast to the cases of CE and EC processes. The general chronopotentiometric and voltammetric responses of a first-order catalytic process are compared. (c) 2005 Elsevier B.V. All rights reserved.