Solvent microextraction (SME) is designed to selectively isolate desired analytes while minimizing the presence of interfering substances in the extracted sample. There are different approaches from which single‐drop microextraction (SDME) can be amalgamated with various analytical methods to enhance its functionalities and improve the analysis of extracted compounds like gas chromatography, and liquid chromatography amplify sensitivity, selectivity, and the capacity to detect trace amounts of analytes in complex matrices. The review focuses on the intricacies of solid‐phase microextraction and elucidates its operational principles. Additionally, it explores various types of SDMEs, detailing their respective benefits, drawbacks, and potential applications in the future. A typical explanation of the construction and working of hollow fiber‐liquid phase microextraction as well as its types has been discussed. The applications of SMEs in the medical and biomedical fields from food analysis to environmental analysis like analysis and purification of water, organic pollutants, drug analysis, and screening of new drugs have been discussed and also illustrated in tabular form. The pros and cons of both analytical techniques are given in a tabular manner as well a broad comparison between different types of advanced SME techniques provides a new direction for environmental monitoring, food safety, and refining of impurities from water samples. The review provides a comprehensive overview of the current progress, recent obstacles, and future possibilities of SMEs in an appropriate manner. Despite numerous promising advancements, the utilization of SMEs remains a challenging field.