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Green Analytical Chemistry (GAC) provides a framework for reducing hazardous reagents, energy consumption, and waste. The topic has gained momentum across many chemical industries over the past 25 years; however, progress in implementing sustainable methods and conducting greenness assessments within forensic laboratories has been comparatively slow. The purpose of this review is to highlight green approaches to analytical separation methods, including greenness assessment metrics, that have been reported in the literature for forensic chemistry and toxicology applications and to raise awareness of GAC in the forensic field. Recent scientific literature highlights promising advances in greener sample preparation and chromatographic approaches, particularly in forensic toxicology and seized-drug analysis. Emerging trends include the use of green solvents, bio-based and deep eutectic solvent systems, and the rapid expansion of microextraction techniques such as SPME, LPME, MEPS, FPSE, and DLLME, which reduce solvent volumes, minimize waste, and support higher-throughput workflows. Parallel developments in portable and miniaturized chromatographic instrumentation such as miniaturized LC–MS systems with increased detection specificity and Lab-on-a-Chip applications show promise for in situ measurements in the field. Ambient ionization mass spectrometry—in particular, DESI and DART—has had a major impact on forensic chemistry by providing tools for the rapid and direct analysis of chemical compounds in complex matrices with little or no sample preparation. Greenness assessment tools—including AGREE, AGREEprep, Eco-Scale, GAPI, and BAGI—are increasingly applied to evaluate analytical methods in forensic chemistry and toxicology, including those used for novel psychoactive substances. Although many green methodologies are well documented, their routine implementation remains limited. The continued integration of green solvents, microextractions, portable instrumentation, and standardized greenness metrics will be essential for advancing sustainable forensic separations.