Air pollution is a great threat to the sustainable development of the world; therefore, the improvement of air quality through the identification and apportionment of emission sources is a significant tool to reach sustainability. Single particle analysis, by means of a scanning electron microscope equipped with X-ray energy dispersive analysis (SEM-EDS), was used to identify the morphological and chemical properties of the PM10 particles in order to identify and quantify the main emission sources in three areas of Lecce, a city in the Apulia region of southern Italy. This type of characterization has not yet been performed for the Lecce site, but it is of particular importance to identify, based on the shape of the particles, the natural sources from the anthropogenic sources that are responsible for the serious health effects of the inhabitants. Three primary schools located in peripheral areas of the city were chosen for the sampling: “School 1” (A site), “School 2” (B site), and “School 3” (C site) to carry out a study of the air quality. The A site is characterized by a greater presence of calcium sulphates probably due both to construction activities present during sampling and to reactions between Ca particles and the sulfur present in the atmosphere. At the C site, there is a relative numerical abundance of different groups of particles that present, in the EDS spectrum, an enrichment in sulfur. At the B site, the number of particle groups is intermediate compared to that of the other two sites. With the source apportionment technique, ten emission sources were identified: combustion, soot, industry, soil, carbonates, sea salt, calcium sulfates, SIA, biological particles, and others. In PM10, the three sites are more affected by the soil source, with an effect greater than 60%.