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Solid phase microextraction (SPME) is a convenient, effective and green sample preparation technique, offering excellent compatibility with different chromatography methods. This review presents an overview of the history of the SPME technique and its early adaptation based on reported patents, followed by some current SPME designs, and intended usage, especially for gas chromatography (GC) applications. Particular focus on quantification approaches in SPME is included, with emphases on the methodology chosen for implementation, correct performance of quantification and validation, and the calibration method. The article concludes by highlighting some innovative SPME-related techniques, some of which are chosen for their quantitative coverage of analytes and their reported applications.