Blood serum from 154 volunteers at 13 UK locations in 2003 were analysed for a range of PCBs, organochlorine pesticides and PBDEs. HCB, p,p′-DDE and p,p′-DDT and β-HCH were the dominant organochlorine pesticides in most samples. BDEs 47, 99, 100, 153, 154 and 183 were the most regularly detected PBDEs. This study is the first report of BDE209 in UK human blood (found in 11 samples, range <15–240 ng/g lipid). Concentration and age correlated for the less easily metabolised PCBs, p,p′-DDT and p,p′-DDE, HCB and HCHs. With increasing age females tended to have lower concentrations of the more chlorinated PCBs than males. Similar PBDE concentrations, and distributions, to those reported in the general population in Sweden in 2002 were found, despite differences in historical PBDE production and usage. There is increasing regulation to control persistent and bioaccumulative chemicals, and establishing human exposure will help to identify substances which should be urgently phased out. A survey of PBDE, PCB and OC pesticide concentrations in human blood helps identify baseline concentrations in the UK population and found decabromodiphenyl ether in non-occupationally exposed individuals.