The construction of highly stable metal–porphyrinic frameworks (MPFs) is appealing as these materials offer great opportunities for applications in artificial light-harvesting systems, gas storage, heterogeneous catalysis, etc. Herein, we report the synthesis of a novel mesoporous metal–porphyrinic framework (denoted as NUPF-1) and its catalytic properties. NUPF-1 is constructed from a new porphyrin linker and a Zr₆O₈ structural building unit, possessing an unprecedented doubly interpenetrating scu net. The structure exhibits not only remarkable chemical and thermal stabilities, but also a distinct structural flexibility, which is seldom seen in metal–organic framework (MOF) materials. By the merit of high chemical stability, NUPF-1 could be easily post-metallized with [Ru₃(CO)₁₂], and the resulting {NUPF-1–RuCO} is catalytically active as a heterogeneous catalyst for intermolecular C(sp³)−H amination. Excellent yields and good recyclability for amination of small substrates with various organic azides have been achieved.