Cationic living polyTHF reacts with primary amine rapidly under ambient conditions. When the amine is in excess the main product is a polymer possessing a terminal secondary amine ligand, and near quantitative conversion is achieved at ten fold excess. The proportion of mono- and disubstituted polymer formed at a given reagent ratio is insensitive to the nature of the amine. Surprisingly, therefore, it is found that the form of the un-neutralized amine product is dependent on the primary amine used, that from aniline exists as the free secondary amine whilst those from cyclohexylamine and n-butylamine exist as the acid salt. A hypothesis is put forward to explain these observations.