From the 1950s to the late 1980s pentachlorophenol (PCP) based anti-sapstain fungicides were widely used in the New Zealand timber industry. Workers involved in treatment, or those handling freshly treated timber, experienced significant PCP exposure. Commercial grade PCP contained contaminants including 2,3,7,8-substituted polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners. To determine whether PCP exposure had resulted in elevated serum dioxin levels twenty years after its use had ceased we tested 94 former sawmill workers randomly selected from surviving members of a cohort enumerated for a mortality and cancer incidence study. After interviewing these individuals to collect demographic data and a comprehensive work history, they were divided into 71 PCP-exposed and 23 non-exposed individuals on the basis of job title and work tasks performed. We compared age-adjusted dioxin levels in the exposed and non-exposed groups, examined the effect of PCP exposure duration and intensity, and compared congener profiles with those found in the commercial grade PCP used at the time. Mean levels in exposed workers were elevated when compared with the non-exposed, with levels of 1,2,3,6,7,8-HxCDD, 1,2,3,4,6,7,8-HpCDD and OCDD being two to three times higher. The congener profiles in serum were consistent with those in PCP solutions, and dioxin levels increased with both employment duration and estimated exposure intensity. Serum dioxin levels in former New Zealand sawmill workers remain elevated twenty years after exposure to PCP ceased, and reflect the pattern of past PCP exposure.