This study provides data on variation in the content of metals and metalloids measured in the lichens (Xanthoria calcicola Oxner) collected in the Syracusan petrochemical complex (Sicily, Italy) which is considered one of the largest in Europe. Concentrations of eighteen trace elements measured in the lichens that were collected from 49 different points were analyzed using an inductively coupled plasma (ICP-MS) device. The concentrations of the typical elements of industrial emissions (As, Cr, Ni, and V) highlight the environmental criticality that exists in the study area. The interpretation of the data in terms of multi-element statistical analysis (FA) and enrichment factor (EFs) proved to be particularly useful in identifying several sources that contribute to the presence of trace elements in the atmospheric particulate between anthropogenic emissions and geogenic emissions. The results of this study reveal the versatility of the lichen species Xanthoria calcicola Oxner in the search for trace elements in highly anthropized environments, so the approach followed in this study can also be applied to other industrial contexts.