Air quality in large cities has worsened in recent years as a consequence people’s health is directly affected. Among the toxic compounds released to environmental air are polycyclic aromatic hydrocarbons (PAHs), nitrated PAHs (nitro-PAHs), and oxygenated PAHs (oxy-PAHs). Performant methods to analyze these compounds is necessary to enable adequate monitoring of air quality. Thus, this manuscript presents the development of a highly sensitive method to analyze PAHs, nitro-PAHs, and oxy-PAHs collected from ambient air (PM) and the gas phase for a period of one year in the urban area of Belo Horizonte, Brazil. PAHs and their derivatives were extracted by cold fiber solid phase microextraction (CF-SPME) and analyzed by gas chromatography coupled to mass spectrometry (GC/MS). The proposed method allows simultaneous analysis of 16 PAHs, nitro-PAHs and oxy-PAHs, presenting very good limits of detection and quantification, as well as appropriate precision and recovery. The results obtained for the period of one year allowed different studies. The compounds collected simultaneously from gas and particulate phase showed that total concentration of 16 PAHs were higher in the gas phase than in the particulate. On the other hand, nitro-PAHs and oxy-PAHs presented similar concentration in gas and particulate phases. The potential carcinogenicity of PAHs relative to benzo[a]pyrene showed benzo[a]pyrene equivalents of 0.49 ng m. The estimated risk of lifetime lung cancer was 5 × 10. Principal component analysis and diagnostic ratio was applied for source distribution indicating that burning of gasoline, diesel and biomass accounted for the PAHs profile in ambient air samples.Copyright © 2020 Elsevier Ltd. All rights reserved.