Abstract: | Porous single crystals which combine ordered lattice structures and disordered inter‐connected pores would provide an alternative to create twisted surface in porous microstructures. Now, transition‐metal nitride Nb4N5 and MoN single crystals are grown on a 2 cm scale to create well‐defined active structures at twisted surfaces. High catalytic activity and stability toward non‐oxidative dehydrogenation of ethane to ethylene is observed. Unsaturated metal–nitrogen coordination structures including Nb‐N1/5, Nb‐N2/5, Mo‐N1/3, and Mo‐N1/6 at the twisted surface mainly account for the C?H activation with chemisorption of H in molecular ethane at the twisted surface, which not only improves dehydrogenation performance but also avoids the deep cracking of ethane to enhance coking resistance. 11–25 % ethane conversion and 98–99 % ethylene selectivity is demonstrated without degradation being observed even after the operation of 50 hours. |