AbstractPositron annihilation spectroscopy (PAS) is a powerful method to study the size and connectivity of pores in zeolites. The lifetime of positronium within the host material is commonly described by the Tao‐Eldrup model. However, one of its largest limitations arises from the simple geometries considered for the shape of the pores, which cannot describe accurately the complex topologies in zeolites. Here, an atomic model that combines the Tao potential with the crystallographic structure is introduced to calculate the distribution and lifetime of Ps intrinsic to a given framework. A parametrization of the model is undertaken for a set of widely applied zeolite framework types (*BEA, FAU, FER, MFI, MOR, UTL), before extending the model to all known structures. The results are compared to structural and topological descriptors, and to the Tao–Eldrup model adapted for zeolites, demonstrating the intricate dependence of the lifetime on the pore architecture.