Quantification of five aliphatic polyamines was performed on a reversed-phase HPLC equipped with a fluorescence detector after dervatizing with 1-naphthyl acetic anhydride (NAAn). The NAAn-derivatized diisopropyl amine (DIPA-NAAn) was the only calibration standard used for quantifying. A model study for the simulation of air sampling was conducted using a Test Atmosphere Generation System for ethylene diamine (EDA) which has the highest vapour pressure amongst the five amines investigated. The collection of EDA in the dynamically generated atmosphere was carried out on NAAn-coated Tenax tubes.