The process of new construction and reconstruction projects in the petrochemical industry is complicated, and the construction accidents have a domino effect. Construction permit-to-work management is an important part of petrochemical engineering, mainly to ensure the identity of workers entering the construction area and permit-to-work qualification. The previous research on permit-to-work management mainly focused on the standardization of the permit-to-work issuing process and the precision of the implementation process rather than specific and implementable technological means. However, with the increase of new construction and reconstruction projects in the petrochemical industry, the traditional and paper-based work permit management model cannot effectively prevent people without working qualifications from entering the construction site at the source, and these solutions do not take into account the compliance, feasibility, and timeliness of the use of qualified permit-to-work. Therefore, from the perspective of brand-new management theory, this study organizes the elements of petrochemical construction permit-to-work management into three levels of product, organization, and process (POP). Then the permit-to-work management system of petrochemical construction based on the POP model is proposed. The face recognition technology is used to realize the real-time dynamic control of the system. The results show that the validity of the petrochemical construction permit-to-work management system based on the POP model in the actual project can realize the transformation permit-to-work from paper to electronic. In addition, it can effectively and quickly verify the permit-to-work qualification of the entry personnel and prevent the retired personnel from returning to the site.