The primary focus of this research was the chemical fractionation of potentially toxic elements (PTEs) and their presence in several industrialised cities in Serbia. Furthermore, their origin, contamination levels, and environmental and human health risks were assessed. The results indicated that the examined soils were characterised by slightly higher Cu, Ni, Pb, and Zn levels than those set by European and national regulations. These elevated Cu, Pb, and Zn concentrations were caused by intensive traffic and proximity to industry, whereas the higher Ni levels were a result of the specific geological substrate of the soil in the study area. The environmental risk was found to be low and there was no enrichment/contamination of the soil with these elements, except in the case of Pb, for which moderate to significant enrichment was found. Lead also poses a potential non-carcinogenic risk to children through ingestion and requires special attention due to the fact that a significant proportion of this element was present in the tested soil samples in a potentially available form. Analysis of the health risks showed that children are more at risk than adults from contaminants and that ingestion is the riskiest exposure route. The carcinogenic risk was within the acceptable limits.