The migration of atomic hydrogen species over heterogeneous catalysts is deemed essential for hydrogenation reactions, a process closely related to the catalyst's functionalities. While surface hydroxyls-assisted hydrogen spillover is well documented on reducible oxide supports, its effect on widely-used nonreducible supports, especially in electrocatalytic reactions with water as the hydrogen source, remains a subject of debate. Herein, a nonreducible oxide-anchored copper single-atom catalyst (Cu