Zirconium-based porphyrinic MOFs (PMOFs, MOF = metal-organic framework) have gained considerable attention in the field of electric/thermo/photo-catalysis as heterogeneous single-site catalysts; however, the study on multisite synergistic catalysis of PMOFs are rare. Herein, we have successfully developed a highly regio- and stereo-selective synthetic method of (E)-β-vinylboronates through hydroboration of alkynes using PCN-222 (Cu, PCN = porous coordination network) as multifunctional heterogeneous catalyst. Compared with homogeneous catalytic system, high TOF value is achieved in the developed method, originating from the synergistic effect of central Cu(II) ions, N atoms of porphyrin rings and terminal –OH groups on Zr-nodes. Notably, density functional theory (DFT) study reveals that five-membered “Cu-N-B-C-C” ring is the key species responsible for the hydroboration process with specific selectivity.