Abstract: Determination of polychlorinated biphenyls (PCBs) is always difficult due to their existence in quite small residue concentration in various environmental media and suffering lots of interference from the complex matrix composition. Therefore, it is essential to select the suitable sample pretreatment methods and advanced detection techniques for analysis of PCBs in environmental samples. This review is focused on the demonstration of characteristics and the main sources of PCBs, the sample pretreatment techniques including ASE, SFE, MAE, SPME, MSPD and the sample purification techniques such as SPE and GPC. The recent development on GC and GC-MS techniques, the most recent applications of some advanced technologies such as GC×GC, fast GC, GC-IT-MS/MS, HRGC-HRMS in PCBs analysis are also presented. This review also summarizes the latest research progress on PCBs analysis worldwide.