Random copolymers of styrene and substituted styrenes bearing arylamino substituents as fluorophore units have been obtained. Their photophysical properties have been investigated by measuring absorption and emission spectra as in solutions as solid-state. All copolymers proved to possess absolute quantum yields up to 0.39 in solution and up to 0.05 in solid-state, depending on their fluorophore substituents. Fluorescence studies have shown that these copolymers show a highly sensitive response towards a diversity of nitroaromatic compounds, both in solutions and in a vapor phase. The detection limits for these compounds towards model nitroaromatic explosives in dichloromethane solution proved to be in the range from 10−6 to 10−7 mol/L. The fluorescent materials prepared by electrospinning of synthesized copolymers have been evaluated as sensor materials for detecting nitrobenzene vapor for our hand-made sniffer with detection limits of 0.5 ppm during 100-s exposure to the vapor. © 2024 Wiley Periodicals LLC.