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Engineering the catalytic activity and stability of materials would require the identification of the structural features that can tailor active sites at surfaces. Porous single crystals combine the ordered lattice structures and disordered interconnected pores, and they would therefore provide the advantages of precise structure features to identify and engineer the active sites at surfaces. Herein, we fabricate porous single-crystalline vanadium nitride (VN) at centimeter scale and further dope Fe (Fe0.1V0.9N) and Co (Co0.1V0.9N) in lattice to engineer the active sites at surface. We demonstrate that the active surface is composed of unsaturated coordination of V-N, Fe-N, and Co-N structures which lead to the generation of high-density active sites at the porous single-crystalline monolith surface. The interconnected pores aid the pore-enhanced fluxion to facilitate species diffusion in the porous architectures. In the nonoxidative dehydrogenation of ethane to ethylene, we demonstrate the outstanding performance with ethane conversion of 36% and ethylene selectivity of 99% at 660°C. Remarkably stability as a result of their single-crystalline structure, the monoliths achieve the outstanding performance without degradation being observed even after 200 hours of a continuous operation in a monolithic reactor. This work not only demonstrates the effective structural engineering to simultaneously enhance the stability and overall performance for practically useful catalytic materials but also provide a new route for the element doping of porous single crystals at large scale for the potential application in other fields.