We herein report a series of microporous metal–porphyrinic frameworks (MPFs), denoted as NUPF-2M, based on rare earth (RE) clusters. NUPF-2M represent the first examples of RE cluster-based MPFs, possessing a rarely seen shp-a topology and exhibiting high thermal and thermal stabilities. After a post-metallization process with FeCl₃, NUPF-2M is catalytically active as an efficient heterogeneous catalyst for intermolecular N–H carbene insertion.