The electrochemical oxidation of paraphenylenediamine (1,4-diaminobenzene, PPD) leads to the passivation of the electrode surface by a thin film as shown by using Cyclic Voltammetry technique. This film can be identified by InfraRed-Attenuated Total Reflectance as a polymeric film of poly(p-phenylenediamine), polyPPD. To establish the mechanism leading from PPD to polyPPD, we performed computations of energy and thermochemical values with the quantum-chemical Self-Consistent Field method at the Hartree-Fock level of theory. Then we compared this mechanism to the ones, previously established with similar ab initio calculations, leading to polyethyleneimine and polypropyleneimine in an attempt to generalize the mechanism of electropolymerization of diamines.