Several epidemiological studies have shown a close relationship between the mass of particulate matter (PM) and its effects on human health. This study reports the identification of inorganic and organic components by attenuated total reflectance-Fourier-transform infrared spectroscopy (ATR-FTIR) analysis in PM10 and PM2.5 filters collected from three air quality monitoring stations in the city of Palermo (Sicily, Italy) during non-Saharan dust events and Saharan events. It also provides information on the abundance and types of water-soluble species. ATR-FTIR analysis identified sulfate, ammonium, nitrate, and carbonate matter characterized by vibrational frequencies at 603, 615, 670, and 1100 cm–1 (SO42–); at 1414 cm–1 (NH4+); at 825 and 1356 cm–1 (NO3–); and at 713, 730, and 877 cm–1 (CO32–) in PM10 and PM2.5 filters. Moreover, aliphatic hydrocarbons were identified in the collected spectra. Stretching frequencies at 2950 cm–1 were assigned to CH3 aliphatic carbon stretching absorptions, while frequencies at 2924 and 2850 cm–1 indicated CH2 bonds. In filters collected during Saharan dust events, the analysis also showed the presence of absorbance peaks typical of clay minerals. The measurement of soluble components confirmed the presence of a geogenic component (marine spray and local rocks) and secondary particles ((NH4)2SO4, NH4NO3) in the PM filters. ATR-FTIR characterization of solid surfaces is a powerful analytical technique for identifying inorganic and organic compounds in samples of particulate matter.