This work describes the synthesis and electrospinning of new fluorescent polymers and their use for the fabrication of optical chemical sensors. A new fluorescent monomer was first synthesized by coupling reactions between methacryloyl chloride and a pyrene derivative, 1-pyrene butanol. Fluorescent polymers containing pyrene molecules were then obtained by the copolymerization of this monomer with methylmethacrylate using 2,2'-azobisisobutyronitrile as the initiator. These polymers show distinct and well-defined fluorescence that is characteristic of the pyrene chromophores. Electrospinning was used to process these polymers into high surface area nanofibrous membranes for optical sensing. The resulting membranes show a high sensitivity to 2,4-dinitro toluene based on the fluorescence quenching of the pyrene chromophores. Fluorescence intensities decreased with increasing concentration of the 2,4-dinitro toluene. The quenching behavior follows Stern-Volmer bimolecular quenching kinetics. The synthesis, characterization, electrospinning fabrication, and sensing capability of these polymers will be discussed.