A mechanism is proposed for the anodic polymerization of ethylenediamine (EDA). Initially, there occurs the formation of the radical cation NH2CH2CH2NH2+. followed by the breaking of the C-N bond, the expulsion of NH2., and concomitant formation of the primary carbocation NH2CH2CH2+ or the aziridinium cation. This cation reacts with an NH2 group of an EDA molecule, yielding a new amine which can be further oxidized. The product on the anode is a polyethyleneimine like polymer. A similar product was found for diethylenetriamine, whose oxidation was studied too. Other pure omega-amines can also polymerize if they are primary amines and have vicinal alkyl groups which are secondary, i.e., have the formula NH2CH2RCH2NH2.