Through a kinetically controlled synthetic process, we synthesized PCN-223, a new porphyrinic Zr-MOF constructed from the newly reported hexagonal prismatic 12-connected Zr-6 cluster through an unusual disordered arrangement, giving rise to the first example of the shp-a network in MOFs. With its extremely high connectivity, PCN-223 shows high stability in aqueous solutions with a wide range of pH. Cationic PCN-223(Fe) formed by postsynthetic treatment is an excellent recyclable heterogeneous catalyst for the hetero-Diels-Alder reaction.