A review and discussion of the analytical developments of the last 10 years in the determination of polychlorinated biphenyls (PCBs) in water are presented, including sample treatment, clean-up, identification and determination. Some of the most significant advances have occurred in the area of sample preparation, such as the increased adoption of solid-phase extraction and on-line techniques and the chromatographic separation of PCB congeners, principally by mass spectrometry. Special attention is focused on applications to real samples.