Abstract The pursuit of catalysts embodying high catalytic activity and long‐term stability remains a dichotomous challenge in the realm of catalysis. Low‐coordination engineering emerges as a promising avenue to escalate catalytic performance. However, these low‐coordination sites mainly exist as defects or edge sites, which are confronted with scarcity, erratic distribution, and notable instability. Here, through meticulous control of reaction kinetics, a long‐range ordered low‐coordination structure has been successfully engineered in catalysts, thereby synergistically amplifying both activity and stability. Employing layered double hydroxides (LDHs) as a paradigm, different from the conventional six‐coordinate structure (M A (O h )M B (O h )), LDHs are designed and synthesized with a low four‐coordinate structure (M A (T d )M B (T d )). The intrinsic activity of Zn(T d )Co(T d ) LDH is remarkably improved by 33.65 times than the traditional six‐coordinated counterpart. Furthermore, the long‐term stability of Zn(T d )Co(T d ) LDH is extended beyond 1600 h. This coordination innovation effectively mitigates the instability associated with highly active sites, offering profound insights for coordination engineering and the synthesis of pragmatic catalysts.