A method using the lipophilic gel Lipidex 5000 for sorption of pentachlorophenol (PCP) from water and urine is described. The procedure for water gives a simultaneous clean-up from lipophilic contaminants and also offers the possibility for determination of less polar compounds, such as 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (p,p'-DDT) and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), collected in a separate fraction. The extracted PCP is derivatized to pentachlorophenyl acetate, which is determined by electron-capture gas chromatography. The average recovery of 0.01-0.15 ng PCP per ml water was 96% and of labelled p,p'-DDT (ca. 5 ng/ml) and TCDD (ca. 0.001 ng/ml) 95 and 92%, respectively. A similar method for enrichment of PCP was applied to acidified urine and to urine hydrolysed with hydrochloric acid or with digestive juice from Helix pomatia. Recoveries of 0.1-2.5 ng PCP per ml non-hydrolysed urine were on an average 92% and of 2.5-10 ng PCP per ml hydrolysed urine 96%. The analyses indicate that PCP in urine from non-occupationally exposed persons is originally conjugated and to some extent liberated when stored. The contamination of organic solvents and laboratory environments with PCP is discussed.