The combustion of plastic waste releases volatile organic compounds (VOCs) that are harmful to human health. However, information on the micro-mechanisms of VOC formation remains lacking. Here, the study hypothesized and verified the relationship between VOC formation and solid component degradation during plastics combustion. The VOCs released during plastics combustion exhibit characteristics such as low carbon content (nc< 10), volatility (9μgm-3 < log10C0 < 11μgm-3), and medium oxidation degree (−1.5 <OSC¯ < −0.5). The dominant VOCs ketones/aldehydes/acids (33-43%) may be attributed to the depolymerization of the polymer structure of plastics, the oxidation of C-O/C=O groups, and the secondary cleavage of gaseous oxygen-containing macromolecules. The VOCs released from the combustion of polyethylene terephthalate (PET) and poly(butyleneadipate-co-terephthalate) (PBAT) contained more aromatics than polyethylene (PE) and polypropylene (PP). And the temperature response of aromatics released from PET and PBAT lagged other VOCs compared that of PP and PE. However, compared to biomass thermal conversion, combustion of plastics releases fewer aromatics and nitrogenous compounds. Collectively, this work shows that the formation mechanisms of VOCs contributed by the solid components during plastic combustion are similar for PET and PBAT due to their similar chemical structures. The proposed mechanism in this paper will provide insight into the control of contaminants during plastic combustion.