Because of the current shortage of first-generation phosgene sensors, increased attention has been given to the development of fluorescent and colorimetric based methods for detecting this toxic substance. In an effort focusing on this issue, we designed the new, second-generation phosgene chemosensor 1 and demonstrated that it undergoes a ring-opening reaction with phosgene in association with color and fluorescent changes with a detection limit of 3.2 ppb. Notably, in comparison with the first-generation sensor RB-OPD, 1 not only undergoes a much faster response toward phosgene with an overall response time within 2 min, but it also generates no byproducts during the sensing process. Finally, sensor 1 embedded nanofibers were successfully fabricated and used for accurate and sensitive detection of phosgene.