Metal single-atom catalysts have attracted widespread attention in the field of lithium-oxygen batteries due to their unique active sites, high catalytic selectivity, and near total atomic utilization efficiency. Isolated metal atoms not only serve as the active sites themselves, but also function as modulators, reversely regulating the surface electronic structure of the support to enhance its inherent electrocatalytic activities. Despite the potential of isolated metal atom-driven active sites, understanding the structure-activity relationship remains a challenge. In this study, we present a ruthenium single-atom doping-driven cost-effective and durable tricobalt tetroxide electrocatalyst with excellent oxygen electrode electrocatalytic activity. The lithium-oxygen battery with this catalyst as the oxygen electrode demonstrates high performance, achieving a capacity of up to 25 000 mA h g-1 and maintaining good stability over 400 cycles at a current density of 100 mA g-1. This improvement is attributed to the exquisite control of the morphology and structure of the discharge product, lithium peroxide. The aresults of physical characterization and theoretical calculations reveal that isolated ruthenium atoms bond with the tetrahedral cobalt site, resulting in spin polarization enhancement and rearrangement of d orbital energy levels in cobalt. This rearrangement reduces the dz2 orbital occupancy and promotes their transfer to the octahedral cobalt site, thereby enhancing its adsorption capacity for the oxygen-containing intermediates, and ultimately increasing the electrocatalytic activity of the oxygen evolution reaction. This work presents an innovative strategy to regulate the catalytic activity of metal oxides by introducing another metal single atom.