Convenient, rapid, and accurate detection of nitroaromatic organic toxins and harmful substances is of great significance in research. In the present study, two-dimensional layered rare-earth hydroxides (LYH) were used as ion-exchange matrix materials, and the anionic fluorescent dye molecules (HPTS) were successfully introduced into the LYH structures in situ via a simple and effective “plug-and-play” strategy, which gave the compounds ultra-sensitive fluorescence sensing detection of nitrobenzene, p-nitrotoluene and p-nitrophenol (Fluorescence response time < 1 sec, and the LOD for nitrobenzene, p-nitrophenol and p-nitrotoluene reached an impressive 349 ppb, 22 ppb and 98 ppb, respectively). Combined with theoretical calculations, we elucidated in detail the fluorescence quenching response mechanism of the LYH-HPTS towards nitroaromatic. Additionally, we also constructed fluorescent paper sensor, which effectively transformed the LYH-HPTS from theoretical detection to device application. The LYH-HPTS material is not only simple to synthesize, cost-effective and stable, but also has the features of fast response, excellent sensitivity and selectivity, and good reproducibility, which provides a new approach for the rapid and accurate detection of nitroaromatic.