The fracture of polymer networks and gels has a significant impact on the performance of these versatile and widely used materials, and a molecular-level understanding of the fracture process is crucial for the design of new materials. Combining molecular dynamics simulations and network analysis techniques, we demonstrate that in the initial undeformed state of model end-linked polymer networks, polymer strands with fewer topological defects in their local surroundings, higher geodesic edge betweenness centrality values compared to the system average, and greater alignment to the loading direction are more prone to breaking under uniaxial tensile deformation.