Molecular simulations provide a powerful means to unravel the complex relationships between network architecture and the mechanical response of polymer networks, with a particular emphasis on rupture and fracture phenomena. Although simulation studies focused on polymer network rupture remain relatively limited compared to the broader field, recent advances have enabled increasingly nuanced investigations that bridge molecular structures and macroscopic failure behaviors. This review surveys the evolution of molecular simulation approaches for polymer network rupture, from early studies on related materials to state-of-the-art methods. Key challenges – including mismatched spatial and temporal scales with experiments, the validity of coarse-grained models, the choice of simulation protocols and boundary conditions, and the development of meaningful structural descriptors – are critically discussed. Special attention is paid to the assumptions underlying universality, limitations of current methodologies, and the ongoing need for theoretically sound and experimentally accessible network characterization. Continued progress in computational techniques, model development, and integration with experimental insights will be essential for a deeper, predictive understanding of polymer network rupture.