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In industrialized countries, there is a growing concern about the possible negative effects on human health induced by high levels of heavy metals in soil. It is recognized that high levels of heavy metals are not necessarily indicative of the adverse effects. These effects are related to bioavailable fractions, which are involved in plant uptake and transfer to the food chain. Bioavailability is a complex issue that is essential to evaluate to determine if heavy metals present in soil may pose hazards to humans and the environment. In the case of direct ingestion of soil, it is essential to consider also bioaccessibility. Bioavailability and bioaccessibility are related to several soil processes and may be largely determined by soil characteristics. This review deals with the influence of soil properties on metal bioavailability and bioaccessibility. A case study on bioavailability and bioaccessibility of heavy metals is reported, considering a large uncontaminated area influenced by deposition from a cement plant.