A laboratory experiment was performed to examine the remobilization of indicator polychlorinated biphenyls (iPCBs) from sediments and its results were applied to the real-world data for explaining the transport of PCBs in river. Seven PCB concentrations were determined in three series of model water–sediment systems (3 g of river sediment, three different volumes of distilled water (0.5, 0.25, and 0.15 ml), and 5 mg of biocide) after 11 days of incubation. Solid-phase extraction was used for separation of analytes from the aqueous phase and solvent extraction for isolation of analytes from the sediments, respectively. The extracts were analyzed for individual iPCB congeners using gas chromatography–mass spectrometry method. For each series of the experiment, the concentrations of PCBs in aqueous phase were similar. The average sediment/water partition coefficient value was 104 l/kg. The solubility of individual PCB congeners in water did not influence the desorption of PCBs from the sediment. Although the dominant form of PCBs in a water–sediment system occurs as suspended and colloidal fractions, these compounds are transported mostly in a dissolved form. Suspended and colloidal matter is a major sink for PCBs in low-energy aquatic environments. In contrast, the dissolved PCBs are readily transported in running waters. The mobilization of PCBs from sediments to aqueous phase, with respect to their solubility in water, seems to be limited, thus reducing the risk of secondary pollution.