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As a highly toxic and widely used chemical, phosgene has become a serious threat to humankind and public security because of its potential use by terrorists and unexpected release during industrial accidents. For this reason, it is an urgent need to develop facile, fast, and selective detection methods of phosgene. In this Article, we have constructed a highly selective fluorescent sensor o-Pab for phosgene with a BODIPY unit as a fluorophore and o-phenylenediamine as a reactive site. The sensor o-Pab exhibits rapid response (15 s) in both colorimetric and turn-on fluorescence modes, high selectivity for phosgene over nerve agent mimics and various acyl chlorides and a low detection limit (2.7 nM) in solutions. In contrast to most undistinguishable sensors reported, o-Pab can react with phosgene but not with its substitutes, triphosgene and biphosgene. The excellent discrimination of o-Pab has been demonstrated to be due to the difference in highly reactive and bifunctional phosgene relative to its substitutes. Furthermore, a facile testing paper has been fabricated with poly(ethylene oxide) immobilizing o-Pab on a filter paper for real-time selective monitoring of phosgene in gaseous phase. [ABSTRACT FROM AUTHOR]