The present invention relates to a method for the purification of cadaverine from an aqueous cadaverine salt composition comprising one or more involatile impurities, the method comprising: (1) mixing the aqueous cadaverine salt composition with one or more bases to provide an aqueous cadaverine composition having a pH of at least about 12; (2) distilling or evaporating the aqueous cadaverine composition to produce an aqueous cadaverine solution, wherein one or more solvents are added to the evaporation/distillation system before the evaporation/distillation stops, and the one or more solvents comprise at least one or more high boiling point (HBP) solvents having a boiling point of at least 185° C. (1 atm); and (3) subjecting the aqueous cadaverine solution to one or more rectification steps to provide a cadaverine product.