Polycyclic aromatic hydrocarbon (PAH) concentrations were determined in 16 topsoils (0–10 cm) collected across the site of a former tar works in NE England. The soils were prepared in the laboratory to two different particle size fractions: <250 μm (fraction A) and >250 μm to <2 mm (fraction B). Sixteen priority PAHs were analysed in the soils using in situ pressurised fluid extraction (PFE) followed by gas chromatography—mass spectrometry (GC–MS). The average total PAH concentration in the soils ranged from 9.0 to 1,404 mg/kg (soil fraction A) and from 6.6 to 872 mg/kg (soil fraction B). These concentrations are high compared with other industrially contaminated soils reported in the international literature, indicating that the tar works warrants further investigation/remediation. A predominance of higher-molecular-weight compounds was determined in the samples, suggesting that the PAHs were of pyrogenic (anthropogenic) origin. Statistical comparison (t-test) of the mean total PAH concentrations in soil fractions A and B indicated that there was a significant difference (95% confidence interval) between the fractions in all but two of the soil samples. Additionally, comparisons of the distributions of individual PAHs (i.e. 16 PAHs × 16 soil samples) in soil fractions A and B demonstrated generally higher PAH concentrations in fraction A (i.e. 65.8% of all individual PAH concentrations were higher in soil fraction A). This is important because fraction A corresponds to the particle size thought to be most important in terms of human contact with soils and potential threats to human health.