The monitoring of heavy metals in industrialized areas to study their association with different occupational and environmental factors is carried out in different ways. In this study, scalp hair analysis was used for the assessment of exposure to these metals in the industrial city of Taranto, characterized by a severe environmental pollution. The highest median values were observed for aluminum, barium, cadmium, lead, mercury, and uranium. Moreover, in the industrial area of Taranto, high levels of barium, cadmium, lead, mercury, nickel, and silver were observed in comparison with other Apulia areas. The risk odds ratios (ORs) for observing values above the 50th percentile were elevated for mercury and fish consumption, uranium and milk consumption, lead and female sex, and aluminum and mineral water consumption. No significant increased risk was observed for occupational activities. In a dendrogram of a cluster analysis, three clusters were observed for the different areas of Taranto (Borgo, San Vito, and Statte). A scree plot and score variables plot underline the presence of two principal components: the first regarding antimony, lead, tin, aluminum and silver; the second regarding mercury and uranium. The observed clusters (Borgo, San Vito, and Statte) showed that lead, antimony, tin, aluminum, and silver were the main component. The highest values above the 50th percentile of these minerals, especially lead, were observed in the Borgo area. The observed metal concentration in the Borgo area is compatible with the presence in Taranto of a military dockyard and a reported increase of lung cancer risk among residents of that area.