In this article, we report a series of hexanuclear rare-earth MOFs based on Ce (III) and 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin, namely Ce-PCN-224, with a new zln topology through linker induce strategy. Ce-PCN224 exhibits permanent porosity, high water and thermal stabilities, and the ability to adsorb dye molecules in the aqueous environment. Moreover, after post-metallation with Fe, Co, and Ni, Ce-PCN-224(Fe) and Ce-PCN224(Co) were proved to be efficient heterogeneous catalysts for the cycloaddition of CO2 with epoxides, attributed to the combination of multiple Lewis acidic sites.