Pressurised liquid extraction (PLE) was used to extract pentachlorophenol from cotton and dyestuffs. Five dyes and one dyed cotton were investigated for pentachlorophenol. The dyed cotton was found to have between 5.3 and 5.9 μg g−1 pentachlorophenol, while the dyes were found to have between 42 and 2569 μg g−1 pentachlorophenol present. The latter were found to be dye and manufacturing site dependant. Recovery experiments, in all cases, were found to be quantitative indicating appropriate sample work-up and manipulations.