A series of highly stable MOFs with 3-D nanochannels, namely PCN224 (no metal, Ni, Co, Fe), have been assembled with six-connected Zr-6 cluster and metalloporphyrins by a linker-elimination strategy. The PCN-224 series not only exhibits the highest BET surface area (2600m(2)/g) among all the reported porphyrinic MOFs but also remains intact in pH = 0 to pH = 11 aqueous solution. Remarkably, PCN-224(Co) exhibits high catalytic activity for the CO2/propylene oxide coupling reaction and can be used as a recoverable heterogeneous catalyst.