<p>Nitroaromatic compounds (NACs), a class of highly toxic and potentially explosive environmental pollutants, have emerged as a critical challenge in ecological monitoring, homeland security, and public well-being. Although various stabilized analytical techniques, such as gas chromatography-mass spectrometry (GC–MS) and high-performance liquid chromatography (HPLC), exist for detecting nitroaromatic compounds (NACs), they often face limitations, including high operational costs, complex instrumentation, challenging handling procedures, and the need for manpower. In this context, luminescent metal–organic frameworks (LMOFs) have garnered significant attention as next-generation sensing platforms due to their high surface area, exceptional structural tunability, and photoluminescent properties. Various instrumental and material-based approaches have been established to investigate and improve the sensing capabilities of MOFs for detecting organic molecules. These strategies aim to refine and expand our understanding of MOFs as sensing probes, improving their limit of detection, sensitivity, and selectivity toward specific analytes. This review comprehensively summarizes recent progress in LMOF-based sensors for nitroaromatic detection, highlighting key design strategies, sensing mechanisms, and performance metrics. Finally, the review outlines prevailing challenges and provides future perspectives to guide the rational design and scalable fabrication of next-generation LMOF sensors for practical deployment in environmental monitoring, forensic analysis, and homeland security applications.</p>