LAUSR

Single atomic catalysts have shown great potential in efficiently electro‐converting O2 to H2O2 with high selectivity. However, the impact of coordination environment and introduction of extra metallic aggregates on catalytic performance still remains unclear. Herein, first a series of carbon‐based catalysts with embedded coupling Ni single atomic sites and corresponding metallic nanoparticles at adjacent geometry is synthesized. Careful performance evaluation reveals NiSA/NiNP‐NSCNT catalyst with precisely controlled active centers of synergetic adjacent Ni‐N4S single sites and crystalline Ni nanoparticles exhibits a high H2O2 selectivity over 92.7% within a wide potential range (maximum selectivity can reach 98.4%). Theoretical studies uncover that spatially coupling single atomic NiN4S sites with metallic Ni aggregates in close proximity can optimize the adsorption behavior of key intermediates *OOH to achieve a nearly ideal binding strength, which thus affording a kinetically favorable pathway for H2O2 production. This strategy of manipulating the interaction between single atoms and metallic aggregates offers a promising direction to design new high‐performance catalysts for practical H2O2 electrosynthesis.