The anodic oxidation of liquid omega -diamine based-electrolyte leads to the passivation of the electrode surface by an insulating film as shown by using an electrochemical quartz crystal microbalance (EQCM) coupled with cyclic voltammetry (CV) technique. These films were identified by infrared-attenuated total reflectance (IR-ATR) as polymeric films: linear polyethylenimine (L-PEI) film for EDA based-electrolyte and linear propylenimine (L-PPI) for 1,3 DAP. We also performed computations of energy and thermochemical values with the quantum-chemical Onsager self-consistent reaction field (SCRF) method at the Hartree-Fock level for modeling the reaction mechanisms leading to the polymeric films.