Abstract Nanocomposite coatings have developed as promising surface-engineering materials for imparting multifunctional properties to textile fabrics, owing to the synergistic effects of their organic and inorganic components. In this study, a β-hydroxyether-naphthoxazine (βhE-NZ) oligomer was prepared by the catalyst-free oligomerization of a difunctional hydroxyl-functional naphthoxazine monomer (NZ-OH) with bisphenol A diglycidyl ether (BADGE), as confirmed by NMR and FTIR spectroscopy.