Ore mineralizations in bedrock and their exploitation may have a negative impact on air quality of surrounding urban areas and, subsequently, on human health. This study uses lichens as bioindicators of atmospheric pollution to evaluate the spatial distribution of potentially toxic elements (PTEs) in the towns close to the massive sulfide deposits of the Iberian Pyrite Belt (IPB) in SW Spain. Altogether 89 native lichen samples of Xanthoria parietina were collected from the mining towns, control towns out of the reach of the mining activity, as well as from distal sampling sites. The samples were analyzed for 29 elements after acid digestion. The concentrations for Co, Ni, Cu, Zn, As, Rb, Mo, Cd, Sn, Sb, Cs, Ba, W, Tl, Pb, S, and Fe are significantly higher in the mining towns in comparison to the control towns. The ore mineral-associated PTEs, including Cu, Zn, As, Ba, and Pb, exhibit extreme concentrations in the urban areas close to the mining activity, and particularly in the small settlement of La Dehesa next to the mineral processing plant and the tailings pond. The distal samples confirm the decrease in the concentrations of all PTEs, and these samples present similar values as in the control areas. The results, point at increased bioaccumulation of PTEs in the lichen thalli of the adjacent urban areas, suggesting that the air quality of the adjacent urban areas is locally impacted by the massive polymetallic sulfide deposits which is enhanced by the mining activity. Therefore, monitoring the urban air quality is recommended. Display omitted •Metal(loid)s were studied in lichen bioindicators in urban areas of mining towns.•High bioaccumulation of sulfide-associated elements was observed in Xanthoria parietina.•Ratios of Cu, Zn, As and Pb were distinct from traffic-related pollution sources.•Potentially toxic elements were significantly higher in mining towns than control towns.