A novel, pyrene‐functionalised copolymer has been synthesised in a single step via imidisation of poly(maleic anhydride‐alt‐1‐octadecene) with 1‐pyrenemethylamine, and its potential for the detection of volatile nitro aromatic compounds (NACs) evaluated. The new copolymer forms complexes in solution with NACs such as 2,5‐dinitrobenzonitrile, as shown by 1H NMR, UV‐vis and fluorescence spectroscopy. Moreover, thin films of this copolymer, cast from THF solution, undergo almost instantaneous fluorescence quenching when exposed to the vapour of 2,5‐dinitrobenzonitrile (a model for TNT) at ambient temperatures and pressures.