Tree barks are relevant interfaces between plants and the external environment, and can effectively retain airborne particles and elements at their surface. In this paper we have studied the distribution of mercury (Hg) in soils and in black pine (Pinus nigra) barks from the Mt. Amiata Hg district in southern Tuscany (Italy), where past Hg mining and present-day geothermal power plants affect local atmospheric Hg concentration, posing serious environmental concerns. Barks collected in heavily Hg-polluted areas of the district display the highest Hg concentration ever reported in literature (8.6 mg/kg). In comparison, barks of the same species collected in local reference areas and near geothermal power plants show much lower (range 19–803 μg/kg) concentrations; even lower concentrations are observed at a “blank” site near the city of Florence (5–98 μg/kg). Results show a general decrease of Hg concentration from bark surface inwards, in accordance with a deposition of airborne Hg, with minor contribution from systemic uptake from soils. Preliminary results indicate that bark Hg concentrations are comparable with values reported for lichens in the same areas, suggesting that tree barks may represent an additional useful tool for biomonitoring of airborne Hg.