Supramolecular solvents (SUPRASs) have rapidly gained more attention as a potential substitute to organic solvents in the sample preparation and pre-concentration process. The essential properties of SUPRAS solvents (e.g., multiple binding sites, different polarity microenvironments, the opportunity to tailor their properties, etc.) these qualities offer numerous opportunities to advance innovative sample preparation and pre-treatment platforms compared to the traditional solvents. Among these qualities, certain importance is placed on theoretical and practical knowledge. That has assisted in making significant developments in SUPRAS that advance our understanding of the processes behind SUPRA'S formation. The SUPRA-solute interactions that drive extractions are explored in this context to develop knowledge-based extraction techniques. This review mainly focused on the significant application of supramolecular-based solvents (SUPRASs) in microextraction techniques.SUPRASs-based liquid-phase microextraction (LPME) is an excellent tool for extracting, simple preparation, and pre-concentration from complex environmental samples. SUPRASs-LPME has a wide range of applications for analysing food, environmental samples, pharmaceuticals, and biological samples.