Molecular dynamics simulation was used to qualitatively and quantitatively discuss the effect of alcoholysis degree on thymol release process in PVA-based antibacterial film to visually exhibit the release process of thymol from the novel PVA/thymol antibacterial packaging film on microscopic level and reveal the release mechanism. PVA/thymol systems with different alcoholysis degrees were constructed by the software Material Studio to simulate the dynamic molecular release of thymol. Antimicrobial releasing process was analyzed considering different parameters, such as the movement of polymer chains, free volume fraction, and diffusion coefficient. The results showed that the diffusion coefficient of thymol molecule was the minimum in completely alcoholized PVA system, the maximum in 88% PVA system, followed by in 78% PVA system. It also showed the motion of thymol molecule in the PVA system was slowly creeping rather than jumping. The difference in alcoholysis degree of the matrix material had influence on the release of antibacterial agents in packaging materials.