Here, we report the chemical characterization and identification of the possible sources of particulate matter (fraction PM10) at two different sites in Naples. PM10 concentration and its chemical composition were studied using the crustal enrichment factor (EF) and principal component analysis (PCA). In all of the seasons, the PM10 levels, were significantly higher (p < 0.01) in the urban-traffic site (denominated NA02) than in the urban-background site (denominated NA01). In order to reconstruct the particle mass, the components were classified into seven classes as follows: mineral dust (MD), trace elements (TE), organic matter (OM), elemental carbon (EC), sea salt (SS), secondary inorganic aerosol (SIA) and undetermined parts (unknown (UNK)). According to the chemical mass closure obtained, the major contribution was OM, which was higher (p < 0.01) during summer than in other seasons. In both sites, a good correlation (R2 > 0.8) was obtained between reconstructed mass and gravimetric mass. PCA analysis explained 76% and 79% of the variance in NA01 and NA02, respectively. The emission sources were the same for both sites; but, the location of the site, the different distances from the sources and the presence and absence of vegetation proved the different concentrations and compositions of PM10.