A novel amino-functionalized polystyrene copolymer (PS-NH2) was designed and synthesized with styrene and 4-vinylbenzyl amine. Additionally, an amino modified glass (G-NH2) was obtained as a carrier. (PS-NH2/pyrene)/G-NH2 fluorescent nanofibrous membrane [named (PS-NH2/pyrene)/G-NH2] was designed and prepared via electrospinning technique to detect representative saturated nitroaromatic (NAC) explosive vapor. The (PS-NH2/pyrene)/G-NH2 showed highly fluorescence stability in ambient condition and further displayed a high quenching efficiency of 70.9% toward trinitrotoluene (TNT) vapor (similar to 10 ppb) with an exposure time of 150 s at room temperature. The abundance of amino groups could effectively adsorb NACs and the binding of electron-deficient NACs to the amino groups on the (PS-NH2/pyrene)/G-NH2 surface led to the formation of charge-transfer complexes. The quenching constant (K-SV) to TNT was obtained to be 1.07 x 10(11) mL/g in gaseous phase with a limit of detection up to 2.76 x 10(-13)g/mL. Importantly, the (PS-NH2/pyrene)/G-NH2 showed notable selectivity toward TNT and 2,4-dinitrotoluene vapors. Straightforwardly, the colorimetric sensing performance can be visualized by naked eye with a color change for detecting of different vapor phase NACs explosives. (C) 2018 Wiley Periodicals, Inc.