Coal tar pitch (CTP) is abundant and widely used, but its properties will be affected due to oxidation aging during storage. In this study, CTP was oxidized by simulating the air oxidation process, and the change of chemical structure has been analyzed by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and both gas chromatography and mass spectrometry (GCMS). The effects of the oxidized and unoxidized CTP co-carbonization with coal on the polycyclic aromatic hydrocarbons (PAHs) emission were detected by GCMS. The small and medium-molecule aromatic substances were reduced during CTP oxidation, while the intermolecular condensation reaction increased the macromolecules content. The catalytic can effectively facilitate the dehydrogenation and condensation reaction of CTP and the entry of oxygen molecules, which leads to the increase of oxygen-containing groups and the decrease of PAHs. Compared to the raw CTP, the catalytic oxidized CTP significantly reduced the emissions of toxic PAHs during the co-carbonization with coal. A possible catalytic mechanism of CTP catalytic oxidation is proposed.