The development of a portable sensor for on-site sensing of 2, 4, 6-trinitrotoluene (TNT) and other nitro aromatics (NAs) is still needed to strengthen environmental protection and public security. Herein, we report the fabrication of fluorescent few-layered MnO₂ nanosheets (FL-MnO₂ NSs) via N,N-dimethyl formamide-mediated ultrasonication and hydrothermal treatment. Electron and spectroscopy studies demonstrate that the modification of the FL-MnO₂ NSs (named as PEI-FL-MnO₂ NSs) with amine-rich polyethyleneimine (PEI) produced planar, β-phase, well-crystalline, and positively charged nanosheets. This PEI-related surface modification not only improves the quantum yield of the FL-MnO₂ NSs from 7.6 to 13.2% but also provides multiple binding sites with nitro groups of NAs. It was found that the presence of TNT, as an example of NAs, efficiently quenched the fluorescence of the PEI-FL-MnO₂ NSs due to the formation of Meisenheimer complexes through the efficient adsorption process. In comparison to PEI-modified MnO₂ quantum dots, the PEI-FL-MnO₂ NSs exhibited relatively high sensitivity to TNT with a limit of detection of 20 pM. By depositing PEI-FL-MnO₂ NSs on a filter paper, the as-made paper sensor was capable of visualizing 10 nM TNT in drinking water and 10 μM TNT on a postal envelope through the appearance of a quenching spot under a UV lamp. Besides, the adsorbed PEI polymer enables the PEI-FL-MnO₂ NSs to electrostatically interact with citrate-capped metal nanoparticles, producing the composites for catalyzing NaBH₄-mediated reduction of NAs. Since the PEI-FL-MnO₂ NSs possess a large surface area to capture NAs and serve as an electron acceptor for BH₄–, the formed composites efficiently catalyze the reaction of NaBH₄ and NAs as compared to metal nanoparticles and PEI-FL-MnO₂ NSs alone.