In the current work, chemical derivatization of amine (NH2) groups with trifluoroacetic anhydride (TFAA) as an analytical method to improve the information scope of X-ray photoelectron spectroscopy (XPS) is investigated. TFAA is known to successfully label hydroxyl (OH) groups. With the introduction of a newly developed gas-phase derivatization protocol conducted at ambient pressure and using a catalyst also NH2 groups can now efficiently be labelled with a high yield and without the formation of unwanted byproducts. By establishing a comprehensive and self-consistent database of reference binding energies for XPS a promising approach for distinguishing hydroxyl from amine groups is presented. The protocol was verified on different polymers, including poly(allylamine), poly(ethyleneimine), poly(vinylalcohol) and chitosan, the latter one containing both types of addressed chemical groups. (C) 2018 Elsevier B.V. All rights reserved.