A theoretical study of the E-DIM reaction with adsorption of the reactants is presented. The electrochemical reaction E can have a heterogeneous (E h ) or surface (E s ) character, whereas the dimerization can occur in a volume near the electrode (DIM v ) or on its surface (DIM s ). Four paths are possible: E h DIM v , E h DIM s , E s DIM h or E s DIM s . The dependence of the variations of the characteristic parameters (e.g.E 1/2 in polarography or RDE voltammetry,E p in LSV), the measurement time (τ,RT/Fv), the concentrationc T or the surface concentrationГ T is different in each case, and can thus be used to determine the nature and the sequence of the paths and to calculate the dimerization reaction rate constant.