Microwave irradiation is a promising technology for the remediation of soil contaminated by organic contaminants. However, the roles of volatilization and decomposition in microwave removal of polycyclic aromatic hydrocarbons (PAHs) in soil have not yet been quantitatively determined. A model describing the removal efficiency of benz(a)anthracene (BaA) at different treatment times and varied conditions was constructed, wherein BaA removal efficiency was positively and linearly correlated with soil temperature. BaA removal in soil was attributed to thermal volatilization (97.8%) and decomposition (2.2%). Radicals such as ∙OH and ∙O 2- were found to initiate BaA decomposition, the pathway of which was elucidated through HPLC-MS analysis, revealing benz(a)anthracene-7,12-dione as the main intermediate product. The new ideas and perspectives founded in this study offer theoretical support for microwave remediation of organic compound-contaminated sites.