Polychlorinated biphenyls (PCBs) are a class of synthetic organic compounds that are used in a wide range of industrial and commercial applications. It has been shown that these molecules are exceptionally stable in the environment, are carcinogenic and neurotoxic, and can cause dermal and ocular complications. Consequently, exposure to PCBs, even at trace levels, can have severe adverse effects on human health and the entire ecosystems. On the other hand, the conventional methods used for the extraction and quantification of PCBs face challenges that have limited their application. Some of such limitations include high consumption of organic solvents, complex multiple-step processes, and low sensitivity. To address these shortcomings, microextraction techniques have been developed as more efficient and greener procedures for the trace analysis of PCBs from different matrices. This research aims at conducting a comprehensive review of the microextraction techniques and analytical methods used for sample preparation and analysis of PCBs in different matrices, along with discussions about the challenges and future prospects.