This study was based on a geochemical soil survey of Stoke-on-Trent in the UK of 747 surface soil samples analysed for 53 elements. A subset of 50 of these soil samples were analysed for their bioaccessible As and Pb content using the Unified Barge Method. Random Forest modelling, using the total element data as predictor variables, was used to predict bioaccessible As and Pb for all 747 samples. Random Forest modelling, using inverse distance weighed predictors and bedrock and superficial geology, was also used to map both total and bioaccessible As and Pb on a 400 × 400 spatial prediction grid with a 50 m resolution. The predicted bioaccessible As ranged from ca. 1 to 8 mg/kg and the total As ca. 8 to 45 mg/kg. The bioaccessible Pb and the total Pb both covered the range ca. 16–1200 mg/kg, with the highest values for both forms of Pb showing similar spatial distributions. Predictor variable importance and information on past industry suggest that the source of both of these elements is driven by anthropogenic causes.