Phosgene, diphosgene, and chlorine are called choking agents due to their acute toxicity to the respiratory system by directly attacking through inhalation and causing acute hypoxia, asphyxia and death. For these reasons, small-molecule fluorescent probes have been developed for their detection to ensure public safety. In this regard, two thiophene-based chemodosimetric fluorescent probes TCAO ((Z)-3-(4-(dimethylamino)phenyl)thiophene-2-carbaldehyde oxime) and HMBT ((Z)-4-(2-((hydroxyimino)methyl)thiophen-3-yl)benzonitrile) were designed, synthesized and characterized using 1H-NMR, 13C NMR, FT-IR spectroscopy and HRMS methods. Probe TCAO exhibited higher selectivity and sensitivity for detecting phosgene than probe HMBT. The electron-donating group (EDG) and electron-withdrawing group (EWG) play a crucial role in detecting phosgene. TCAO, bearing EDG, exhibited a fluorescence 'turn-on' response by the NGP-assisted conversion of aldoxime to the cyano group in the presence of phosgene; whereas HMBT, bearing EWG, did not show any fluorometric response. Therefore, further studies were conducted on TCAO, and the quantum yield changed from Φ = 0.043 to Φ = 0.155 in the presence of phosgene. The limit of detection for TCAO was estimated to be as low as 51 nm. In addition, onsite monitoring for visual detection was performed using the easy-to-handle paper-strip method.