In this paper, we aim to explore the operational performance of a green closed-loop supply chain under random events. A green closed-loop supply chain model based on generalized stochastic Petri nets (GSPN) is built using the Petri nets theory. According to the isomorphic relationship between GSPN and continuous-time Markov chains, the relevant Markov model is converted from GSPN, and the steady-state probability of the model is then calculated. Finally, the model is analyzed from the aspects of time performance and operation efficiency of each link. Compared to previous studies, this paper finds that: when the whole green closed-loop supply chain system reaches a dynamic equilibrium state, the product has a steady-state probability at all stages, and thus the overall operational performance of the system can be obtained; compared with the recycling of waste products, the green product takes a longer time in the production and distribution stages; since marketing, packaging processing, market feedback, and market demand formulation account for a high level of utilization throughout the life cycle of green products, decision makers need to focus on the supervision and management of these links. Managers of green closed-loop supply chain systems need to adjust their decision-making strategies in a timely manner according to the performance level of the system in the steady state to realize the efficient operation of the system. This paper not only provides theoretical support for the improvement of the operational efficiency of green closed-loop supply chain system, but also provides new ideas for the research of green closed-loop supply chain operation mode.