Thirty-two brownfield sites from the city of Wolverhampton were selected from those with a former industrial use, wasteland or areas adjacent to industrial processes. Samples (<2 mm powdered soil fraction) were analysed, using inductively coupled plasma-atomic emission spectrometry (ICP-AES) for 20 elements. Loss on ignition and pH were also determined. A five-step chemical sequential extraction technique was carried out. Single leach extraction with 0.12 M hydrochloric acid of Pb, Cu and Zn in soil was determined as a first approximation of the bioavailability in the human stomach. Some of the sites were found to have high concentrations of the potentially toxic elements Pb, Zn, Cu and Ni. The partitioning of metals showed a high variability, however a number of trends were determined. The majority of Zn was partitioned into the least chemically stable phases (steps 1, 2 and 3). The majority of Cu was associated with the organic phase (step 4) and the majority of Ni was fractionated into the residue phase (step 5). The majority of Pb was associated with the residue fraction (step 5) followed by Fe-Mn oxide fraction (step 3). The variability reflects the heterogeneous and complex nature of metal speciation in urban soils with varied historic histories. There was a strong inverse linear relationship between the metals Ni, Zn and Pb in the readily exchangeable phase (step 1) and soil pH, significant at P < 0.01 level. There was a significant increase (P < 0.05) in the partitioning of Cu, Ni and Zn into step 4 (the organic phase) in soils with a higher organic carbon content (estimated by loss on ignition). Copper was highly partitioned into step 4 as it has a strong association with organics in soil but this phase was not important for the partitioning of Ni or Zn. The fractionation of Ni, Cu and Zn increased significantly in step 3 when the total metal concentration increases (P < 0.01). The Fe-Mn oxide fraction becomes more important in soils elevated in these metals, possibly due to the scavenging of metals by oxides. Cu and Pb extracted by HCl was statistically similar to the sum of the metals in steps 1 to 4 (P < 0.01) and HCl available Zn was statistically similar to the sum of Zn in steps 1 to 3 (P < 0.01). Step 4 (the organic phase) was not an important phase for Zn, so it was concluded that any Cu, Zn and Pb present in soil in a nonresidue phase would be potentially available for uptake into the human system once soil has been ingested.