Magnetic fractions (MFs) in industrially derived contaminated soils were extracted with a magnetic separation procedure. Total, soluble, and bioaccessible Cr, Cu, Pb and Zn in the MFs and non-magnetic fractions (NMFs) were analyzed using aqua regia and extraction tests, such as deionized water, toxicity characteristic leaching procedure (TCLP), and gastric juice simulation (GJST) test. Compared with the non-magnetic fractions, soil MFs were enriched with Fe, Mn, Pb, Cd, Cr, Cu, and Ni. Extraction tests indicated that soil MFs contained higher water, TCLP, and GJST-extractable Cr, Cu, Pb, and Zn concentrations than the soil NMFs. The TCLP-extractable Pb concentration in the MFs exceeded the USEPA hazardous waste criteria, suggesting that soil MFs have a potentially environmental pollution risk. Solubility of trace metals was variable in the different extraction tests, which has the order of GJST > TCLP > water. TCLP test showed Cu and Zn were more mobile than Cr and Pb while bioaccessibility of trace metal defined by GJST test showed the order of Cu ≈ Cr ≈ Zn > Pb. These findings suggested that the MFs in the industrially derived contaminated soils had higher possibility of polluting water bodies, and careful environmental impact assessment was necessary.