Polychlorinated biphenyls (PCBs) have gained much attention for their carcinogenic, teratogenic, and mutagenic properties. Although banned in the 1970s, PCBs are still frequently found worldwide in environment, animal-origin food and natural waters. Therefore, the development of determination methods is an indispensable step for the monitoring of PCBs. Surface-enhanced Raman spectroscopy (SERS) is an emerging technique for the chemical analysis. With the advantages of excellent sensitivity and significant enhancement to identify the target, SERS has become a promising alternative method for PCBs analysis. This paper comprehensively reviews the recent progress of SERS development in the determination of PCBs, mainly focusing on the preparation of SERS substrates. As the current SERS research on PCBs analysis is still in an early stage, there are several hurdles for further advancing SERS for complex samples. This review includes our discussion on the current challenges and outlook on real-word applications of SERS in PCBs analysis.