Twenty-four surficial sediment samples, representing different environments within the Venice Lagoon, were analyzed for polychlorinated biphenyls (PCBs) in order to assess degrees of pollution, sources, areal distribution, and potential risk for the environment. Concentrations in surficial sediments range from 2 to more than 2049 μg kg −1 dw. The maximum is probably due to the discharge of industrial wastes into the Brentella Canal, within the first Industrial Area. Lagoon samples are 11–205 times less contaminated, being influenced by pollutants stored in the canals only occasionally. Congener profiles distinguish PCBs in two main categories. The baseline pollution is probably due to a variety of sources within the lagoon system, whereas less chlorinated PCBs were discharged into the Brentella Canal. Our estimates suggest that, due to high concentrations, toxic equivalents (TEQs) of PCBs are comparable to those relative to PCDD/Fs for the least contaminated samples, whereas they are lower in case of heavy PCDD/F contamination.