Green chem. principles have been incorporated into various disciplines of chem., including anal. chem., as an ongoing awareness and interest in the state of the ecosystem. The neg. impacts of anal. procedures may cause environmental damage and pose major threats to operators. Therefore, it is critical to consider the consequences and the implications of researchers′ and users′ activities of anal. techniques. This review provides a comprehensive overview of the history of Green Anal. Chem. (GAC) and the existing greenness assessment metric tools, including criteria, concepts, principles, fundamentals, strengths, and weaknesses (merits and demerits). Addnl., a comparison between the metric tools is given, and their relevance in various anal. approaches is explored. For the first time, ten greenness appraisal approaches are thoroughly investigated, conveyed, and implemented. These ten approaches comprise the following: National Environmental Method Index (NEMI), Modified NEMI, anal. Eco-Scale, HPLC-EAT (Environmental Assessment Tool), Anal. Method Volume Intensity (AMVI), Green Anal. Procedure Index (GAPI), Complementary Green Anal. Procedure Index (ComplexGAPI), Anal. Method Greenness Score (AMGS) Calculator, Anal. Greenness (AGREE), Anal. Greenness for sample preparation (AGREEprep), and other assessment tools. Furthermore, the applicability of the discussed assessment tools is examined by evaluating some research articles for determining pharmaceutical residues in water as a case study. With this review, researchers′ knowledge to comprehend and remain fully up-to-date with the current greenness evaluation tools is expanded, and selecting and applying the most appropriate approach through a realistic appraisal and comparison of the tools are realized.