Water environment pollution is becoming an increasingly serious issue due to industrial pollutants with the rapid development of modern industry. Among many pollutants, the toxic and explosive nitroaromatics are used extensively in the chemical industry, resulting in environmental pollution of soil and groundwater. Therefore, the detection of nitroaromatics is of great significance to environmental monitoring, citizen life and homeland security. Lanthanide–organic complexes with controllable structural features and excellent optical performance have been rationally designed and successfully prepared and used as lanthanide-based sensors for the detection of nitroaromatics. This review will focus on crystalline luminescent lanthanide–organic sensing materials with different dimensional structures, including the 0D discrete structure, 1D and 2D coordination polymers and the 3D framework. Large numbers of studies have shown that several nitroaromatics could be detected by crystalline lanthanide–organic-complex-based sensors, for instance, nitrobenzene (NB), nitrophenol (4-NP or 2-NP), trinitrophenol (TNP) and so on. The various fluorescence detection mechanisms were summarized and sorted out in the review, which might help researchers or readers to comprehensively understand the mechanism of the fluorescence detection of nitroaromatics and provide a theoretical basis for the rational design of new crystalline lanthanide–organic complex-based sensors.