This study demonstrated the applicability of laser-induced breakdown spectroscopy (LIBS) to determine elements (C, H, and O) and their ratios of aerosols, enabling to discriminate various types of carbonaceous aerosols. The elements of carbonaceous aerosols which were collected on Ag membrane filter under Argon environment were successfully detected by using the LIBS. The LIBS responses (emission lines of C, H, and O in the LIBS spectra) to increasing carbonaceous aerosols were evaluated. The sensitivity of emission lines varied with different elements. Limit of detection (LOD) values for C, H, and O elements for aerosols collected on the filter were found to be 3.17 μg, 0.15 μg, and 2.25 μg, respectively. The spectral data (elemental ratios) obtained using LIBS were in reasonable agreements with the nominal atomic ratios (H/C and O/C) of various carbonaceous aerosols. Further, LIBS spectra were investigated by using principal component analysis (PCA) method to identify types of various carbonaceous aerosols. Our results suggested the possibility of the LIBS technique to detect and/or to discriminate various carbonaceous aerosols and to determine their elemental ratios (H/C and O/C).