Electroanalytical and chromatographic methodologies have been applied for the determination of pentachlorophenol (PCP) and some of its derivatives in real soil samples contaminated by industrial discharge. The analytes were extracted with hexane from soil samples collected at different points of the site and mixed to produce a representative sample. Square wave voltammetry (SWV) experiments were carried out on either a boron-doped diamond (BDD) electrode or a gold ultramicroelectrode (Au-UME) in an analyte composed by the Britton-Robinson (B-R) buffer at pH 5.5 with the direct addition of proper amounts of the extract. The voltammetric responses revealed an irreversible anodic peak at approximately 0.80 V vs. Ag/AgCl with a peak current showing a linear dependence on PCP concentration. This linear relationship yielded a detection limit (DL) of 2×10^-8 mol l^-1 (or 5.5 μg l^-1) for the BDD electrode and 6.9×10^-8 mol l ^-1 (18.4 μg l^-1) for the Au-UME, while the independently measured HPLC detection limit was 1.1×10^-8 mol l^-1 (3.0 μg l^-1). The application of electroanalytical and chromatographic methodologies in the analysis of soil extracts revealed, besides the PCP responses, signals for some related molecules such as o-tetrachlorobenzoquinone (o-chloranil), hexachlorobenzene and tetrachlorophenol. Recovering experiments for PCP showed a concentration of 27.5 mg kg^-1 for the electroanalytical determinations and 26.8 mg kg ^-1 for the HPLC analysis, values exceedingly high if considering that the maximum residue limit established for natural waters by the Brazilian Environmental Agency is 10 μg l^-1.