The separation of polyethylene polyamines by various forms of chromatography has been studied. Ethylenediamine is easily separated from the higher polyamines by thin-layer chromatography and by ion-exchange chromatography. Diethylenetriamine, triethylenetetramine and tetraethylenepentamine can be separated by gas-liquid chromatography on Teflon powder coated with 5% SE-30, and on a larger scale by ion-exchange chromatography. The latter technique involves absorption on AG-50X8, development with 2 M hydrochloric acid, and elution with 6% ammonia solution.