Some organic pollutants including polychlorinated biphenyls (PCBs), polybrominated diphenylethers (PBDEs) and hexachlorobenzene (HCB) have been banned from production and use in the UK for > 30 years but due to their toxicity and persistence are still of concern. However, due to their hydrophobicity they are present at very low concentrations and are difficult to measure in water, and so other matrices need to be sampled in order to best assess contamination. This study measured concentrations of ΣICES 7 PCBs (PCB congeners 28, 52, 101, 118, 138, 153 and 180) and Σ6 PBDEs (PBDE congeners 28, 47, 99, 100, 153, 154) and HCB in both bed-sediments and wild roach (a common pelagic fish) in the Thames Basin. The highest sediment concentrations were detected in an urbanised tributary of the Thames, The Cut at Bracknell (HCB: 0.03–0.40 μg/kg dw; ICES 7 PCBs: 4.83–7.42 μg/kg dw; 6 BDEs: 5.82–23.10 μg/kg dw). When concentrations were expressed on a dry weight basis, the fish were much more contaminated than the sediments, but when sediment concentrations were normalised to organic carbon concentration they were comparable to the fish lipid normalised concentrations. Thus, despite the variability in the system, both sediments and wild fish can be considered suitable for representing the level of POPs contamination of the river system given sufficient sample numbers.