Novel multifunctional fluorescent chemosensors composed of electrospun (ES) nanofibers with high sensitivity toward pH, mercury ions (Hg), and temperature were prepared from poly(-Isopropylacrylamide---methylolacrylamide--rhodamine derivative) (poly(NIPAAm--NMA--RhBN2AM)) by employing an electrospinning process. NIPAAm and NMA moieties provide hydrophilic and thermo-responsive properties (absorption of Hg in aqueous solutions), and chemical cross-linking sites (stabilization of the fibrous structure in aqueous solutions), respectively. The fluorescent probe, RhBN2AM is highly sensitive toward pH and Hg. The synthesis of poly(NIPAAm--NMA--RhBN2AM) with different compositions was carried on via free-radical polymerization. ES nanofibers prepared from sensory copolymers with a 71.1:28.4:0.5 NIPAAm:NMA:RhBN2AM ratio ( ES nanofibers) exhibited significant color change from non-fluorescent to red fluorescence while sensing pH (the λ exhibited a 4.8-fold enhancement) or Hg (at a constant Hg concentration (10 M), the λ of exhibited 4.7-fold enhancement), and high reversibility of on/off switchable fluorescence emission at least five times when Hg and ethylenediaminetetraacetic acid (EDTA) were sequentially added. The ES nanofibrous membranes had a higher surface-to-volume ratio to enhance their performance than did the corresponding thin films. In addition, the fluorescence emission of ES nanofibrous membranes exhibited second enhancement above the lower critical solution temperature. Thus, the ES nanofibrous membranes prepared from with on/off switchable capacity and thermo-responsive characteristics can be used as a multifunctional sensory device for specific heavy transition metal (HTM) in aqueous solutions.