A family of multivariate metal-organic frameworks (MOFs) with three-kinds of orderly distributed metals were designed and successfully synthesized by combining metalloporphyrin sheets and pentafluoride (NbOF5)2- pillars. Benefiting from the cooperative nature of open-metal-sites (OMSs) within porphyrins, specific pore-sizes, coupled with fluorine-rich electrostatic environments, the fabricated materials demonstrated high affinity toward CO2, and good catalytic performance, structural robustness, and good recyclability for the conversion of epoxides and CO2 to cyclic carbonates at room temperature and 1 atm pressure.