Western Macedonia, located in North-western Greece, is largely dominated by lignite mining and lignite-fired power plants, which are a significant part of the country’s economy. However, the electricity generation and the related activities are among the greatest sources of air pollutants. In this study, we focus on the air quality of Western Macedonia based on measurements of Particulate Matter (PM2.5 and PM10) over a 12-year period (from 2010 to 2021) and a sampling of PM-bound trace elements over the course of 12 months (from December 2017 to November 2018). The analysis revealed an overall decrease of PM2.5 and PM10 concentrations over the study period. In general, the concentrations of PM exhibited seasonality patterns associated with the weather conditions and the local sources of air pollutants. These major sources of air pollution are the lignite mining processes, the emissions from the lignite-fired power plants, and the anthropogenic emissions from the biomass burning and heating systems. In addition, the analysis of the PM-bound trace elements revealed some differences; the elemental profiles of both PM2.5 and PM10 were quite similar, while the most abundant elements (Ca and Si) indicate that the main emission sources were related with the mining activities and the coal combustion.