Solid-phase microextraction (SPME) was developed to address the need for rapid sampling and sample preparation, both in the laboratory and on-site. Unlike traditional sample preparation methods, SPME is a non-exhaustive extraction technique in which only a small portion of the target analyte is removed from the sample matrix. Therefore, calibration of SPME for quantitative analysis is very important. In this review, we summarized the proposed SPME calibration methods and the characteristics of these methods were discussed.