Abstract: This invention relates to a process for separating mono-n-hexylamine from water and particularly to an improvement in a process for the recovery of mono-n-hexylamine from the reaction of n-hexanol with ammonia under amination conditions. In this process water is produced as a by-product and in the separation process an azeotrope is formed which comprises about 49% water and 51% hexylamine. The process for enhancing separation of the azeotrope of mono-n-hexylamine and water comprises contacting the azeotrope of mono-n-hexylamine and water with di-n-hexylamine or with a mixture of di-n-hexylamine and tri-n-hexylamine in sufficient amount to reduce the solubility of mono-n-hexylamine in water thus forming an organic phase and an aqueous phase which can be separated by simple techniques, e.g., decanting.