To create active sites on surfaces, the identification of structural features that could confine the local‐defect structure in the lattice is required. Porous nitride single crystals, combining the advantages of porosity and structural coherence, provide the possibility to create coordinatively unsaturated metal–nitrogen active sites confined on surfaces. For the first time, ordered active sites and tailor the atomically resolved Fe−N and Co−N local structures are created through control of the unsaturated nitrogen coordination at twisted surfaces in porous single‐crystalline FenN (n=2–4) and ConN (n=1–3) nanocubes. The precise tailoring of the electronic structures of these coordinatively unsaturated active sites therefore engineer the catalytic activity. Optimum electrocatalysis performances are observed with the porous Fe4N and Co3N nanocubes with highly unsaturated nitrogen coordination for selective nitrate reduction to ammonia and nitrobenzene amination to aminobenzene, while the structural coherence of these porous nitride single crystals delivers excellent durability.