The asymmetric epoxidation of unfunctionalized olefins using Jacobsen’s catalyst is an effective strategy to achieve chiral epoxides. We report Jacobsen’s catalysts anchored onto ZnPS-PVPA upon alkyldiamines as active heterogeneous catalysts for the epoxidation of unfunctionalized olefins (conv%, up to >99; ee%, up to >99). These new heterogenized catalysts not only could be reused nine times with no variation in performance but also display high performance in large-scale reactions, which presents practical applications in high-throughput organic chemistry.