The voltammetric lability of a complex system, where a metal ion M and a ligand L form the species ML and ML2, is examined. Together with the rigorous numerical simulation of the problem, two limiting cases are analysed for the overall process ML2 → M: (i) the most common case for aqueous complexes, where ML → M is the kinetically limiting step and (ii) the case where ML2 → ML is limiting. In both cases, analytical expressions for the lability criteria are provided which show good agreement with the results obtained from the rigorous numerical simulation of the problem.