The potentiodynamic behaviour of Ag in 0.1 M NaOH in the potential range of Ag2O electroformation is investigated through the application of different potential/time perturbation programmes. The splitting of the electroreduction profile which is produced under well-defined perturbation conditions and the shift of the Ag2O electroreduction E/i profile under a constant charge condition, suggest that ageing-type processes are involved in the overall electrochemical reaction. These processes are related to a probable dehydration of the Ag2O multilayer.