Through topology-guided synthesis, a Zr-based mesoporous MOF was successfully constructed, adopting a β-cristobalite-type structure. The MOF is embedded with well-arranged terpyridine coordination sites for facile post-synthetic metalation, and can be effectively used as a general scaffold for the preparation of noble-metal-free catalysts. For instance, the scaffolded metal@MOF material exhibits highly efficient catalytic activity for alkene epoxidation and arene borylation.