The research is devoted to the investigation of the selectivity detection of 16 polycyclic aromatic hydrocarbons (PAHs) using gas chromatography-mass spectrometry (GC-MS), electron ionization (EI) GC-MS with atmospheric pressure photoionization (APPhI) and GC-MS atmospheric pressure photochemical ionization (APPhCI) when vapors of different substances (benzene, toluene, and naphthalene) were used as gas reagents. Capillary columns of different lengths were used for the separation of the components of the mixture of 44 semivolatile organic compounds. It was shown that the most-selective detection of 16 PAHs in a 44- component mixture was possible when GC-MS APPhCI was used. Only 16 PAHs were registered on the respective mass chromatograms and a fast detection of them was possible. The respective APPhI and APPhCI mass spectra consisted of only peak of the respective molecular ion, M⁺⁺ - the radical cation. Detection limits were 3 pg μL⁻¹ to 15 pg μL.