The aim of this study was to determine the concentrations of arsenic (As), cadmium (Cd), chromium (Cr), mercury (Hg), manganese (Mn), lead (Pb), and vanadium (V) in soil and chard samples collected in various industrial sites of Tarragona County (Spain), an area with an important number of petrochemical industries. Samples were also collected in urban (Tarragona downtown) and presumably unpolluted (blank samples) sites. Human health risks derived from metal inhalation and ingestion of soils were also assessed. With the exception of an increase in the levels of Cd and V, significant differences in soil samples from the industrial and the unpolluted zone were not found. In chard samples, significant differences between collection sites were only noted for V concentrations. For non-carcinogenic risks, the current levels of metals in the industrial area were lower than those considered as safe for the general population. In relation to carcinogenic risks, only As ingestion and Cr inhalation in the industrial zone might potentially cause an increase of the cases of cancer. A Kohonen self-organized map (an Artificial Neural Network) showed differences in metal concentrations according to the zone of origin of the samples. The current results suggest that although in general terms the petrochemical complex is not a relevant metal pollution source for the area, attention should be paid to As, Cr and V.