Persistent organic pollutants (POPs) are a global concern due to their ubiquitous presence and toxicity. Currently, there is a lack of information regarding POPs from South Africa. Here we report and interpret concentrations of polychlorinated dibenzo- p-dioxins (PCDDs), -dibenzofurans (PCDFs) and co-planar-biphenyls (PCBs) in soils and sediments collected from central South Africa. High resolution gas chromatography–high resolution mass spectrometry (HRGC/HRMS) and the H4IIE- luc bio-assay were used to identify and quantify individual PCDD/F congeners and to report the total concentration of 2,3,7,8-tetrachloro dibenzo- p-dioxin equivalents (TCDD-EQ), respectively. TCDD-EQs determined by use of the bio-assay, and concentrations of WHO 2005-TEQ (toxic equivalents) determined by chemical analysis, were similar. The limit of detection (LOD) for the bio-assay was 0.82 and 2.8 ng TCDD-EQ kg −1, dw for sediment and soil, respectively. EQ20 concentrations determined by use of the bio-assay ranged from <LOD to 70 ng TCDD-EQ kg −1, dw for soil, and from <LOD to 45 ng TCDD-EQ kg −1, dw for sediment. Concentrations of WHO 2005-TEQ in soils were generally greater than those in sediments, and soils from the industrial area of Vanderbijlpark and the residential area of Klerksdorp contained the greatest concentrations. Based on the congener-specific HRGC/HRMS analyzes, concentrations of WHO 2005-TEQ ranged from 0.12 to 32 ng WHO 2005-TEQ kg −1, dw in sediments, and between 0.34 and 20 ng WHO 2005-TEQ kg −1, dw in soils. The sources, processes and threats that govern and are associated with the lesser concentrations in sediment and greater concentrations in soils need further investigation.