A procedure to identify the parameter set of electrochemical models involving adsorption-desorption of intermediates species, employing impedance measurements, is presented. Two steps are considered. First, the theoretical structural identifiability analysis of the model is carried out to know the number of parameter sets. which give the same potential/current model behavior. Second, using steady state and electrochemical impedance measurements, the parameter identification procedure based on interval analysis is carried out to identify one of the possible solutions. Accordingly, all possible parameter sets giving the same potential/current behavior are obtained. The application of structural and parametric identification procedures is discussed for the Volmer-Heyrovsky model associated with the hydrogen evolution reaction (HER).