Li‐oxygen batteries have attracted much attention due to its ultra‐high theoretical specific capacity, but the discharge product Li2O2 is easy to accumulate, leading to low battery stability. Here, we demonstrate a series of high‐efficiency cathode catalysts of Co3O4 loaded with single‐atomic metals (M=Ru, Pd, Pt, Au, Ir). The single‐atomic metal could substitute the central Co atom in the octahedral coordination structure and maintain the structural stability; benefiting from the electron promoter effect, rendering more highly active Co3+ exposed, providing rich nucleation sites for Li2O2 deposition. And the loaded M atoms could separate the active Co3+ centers, thereby regulating the dispersion of Li2O2 to obtained a sheet‐like morphology, which could facilitate its decomposition in the subsequent charge cycle. Our work found that the single atoms could effectively modulate the active metal oxide with which it is coordinated, thus collectively boosting the catalytic performance.

Li‐oxygen batteries have attracted much attention due to its ultra‐high theoretical specific capacity, but the discharge product Li2O2 is easy to accumulate, leading to low battery stability. Here, we demonstrate a series of high‐efficiency cathode catalysts of Co3O4 loaded with single‐atomic metals (M=Ru, Pd, Pt, Au, Ir). The single‐atomic metal could substitute the central Co atom in the octahedral coordination structure and maintain the structural stability; benefiting from the electron promoter effect, rendering more highly active Co3+ exposed, providing rich nucleation sites for Li2O2 deposition. And the loaded M atoms could separate the active Co3+ centers, thereby regulating the dispersion of Li2O2 to obtained a sheet‐like morphology, which could facilitate its decomposition in the subsequent charge cycle. Our work found that the single atoms could effectively modulate the active metal oxide with which it is coordinated, thus collectively boosting the catalytic performance.