Electroanalytical techniques like cyclic voltammetry allow convenient and fast identification of the redox status and stability of the intermediates generated at electrodes in electrosynthetic processes. Accordingly, reliable mechanistic features can also be derived from the electrochemical characterization of the reactive species, and in some cases complete and complex mechanisms can be disclosed. This minireview highlights some representative examples taken from metal-catalyzed electroreductive processes where simple electrochemical approaches provide essential information on the nature and the fate of the species formed. A special focus is made on cobalt-promoted electrosynthetic processes owing to the broad range of situations they display towards the stability of electrogenerated species, their reactivity and the possible follow-up reactions.