<p>Nitro compounds (NCs) are a class of organic pollutants with significant environmental and health risks, including toxicity, carcinogenicity, and mutagenicity. Despite their limited solubility in water, their widespread use in explosives, dyes, agrochemicals, and pharmaceuticals has led to persistent contamination of aquatic systems. The detection of NCs in water is challenging due to their low concentrations and the complexity of environmental matrices. This review summarizes current advances in analytical methods for the determination of nitro-based explosives in water, with emphasis on recent developments in sample preparation and extraction techniques. Classical approaches such as solid-phase extraction (SPE) are compared with miniaturized and solvent-saving methods including solid-phase microextraction (SPME), dispersive liquid–liquid microextraction (DLLME), and single-drop microextraction (SDME). Innovative approaches employing deep eutectic solvents (DESs) and magnetic materials are also highlighted. These greener techniques not only reduce solvent consumption (e.g., SDME using as little as 3 μL of solvent) but also solidification of aqueous drop solid-phase extraction (SADSPE) demonstrate high analytical performance, achieving detection limits in the ng/L to μg/L range. Environmental sustainability has increasingly been quantified using green chemistry metrics such as AGREE, AGREEprep, and AESA, with several techniques scoring above 70%, confirming their alignment with sustainable analytical practices. By integrating a decade of progress, this review identifies research gaps, evaluates method efficiency and scalability, and underscores the importance of greener, high-sensitivity techniques for monitoring explosive residues in water. These trends support both environmental protection and compliance with evolving global regulations.</p>