In this work, the content of polycyclic aromatic hydrocarbons (PAHs) in total suspended particles and particulate matter with an aerodynamic diameter ≤ 2.5 µm (PM2.5) was analyzed using gas chromatography-mass spectrometry. In addition, a sequential chemical analysis of C-rich particles was performed through the parallel coupling of micro-Raman spectroscopy and scanning electron microscopy with X-ray scattering detection. Samples were collected at four sites in the Monterrey metropolitan area, Mexico. A total of 13 PAHs were quantified; indeno(1,2,3-cd)pyrene, chrysene, and benzo(a)anthracene were the most abundant. The total PAH concentrations at the four sampling sites ranged from 1.34 to 8.76 μg/m3. The diagnostic relation of the PAHs indicates that these compounds were emitted by the burning of gasoline and diesel and by the burning of charcoal and biomass. The sequential analysis correlated the morphology and the elemental/molecular composition of the C-rich particles, associated with the PAHs, with their possible emission sources. The estimated lifetime excess cancer risk for inhalation was higher than that established by the World Health Organization, which clearly makes this a potential health risk for the population.