Solid-state Li-O2 batteries (SSLOBs) have attracted considerable attention because of their high energy density and superior safety. However, their sluggish kinetics have severely impeded their practical application. Despite efforts to design highly efficient catalysts, efficient oxygen reaction evolution at gas-solid interfaces and fast transport pathways in solid-state electrodes remain challenging. Here, we develop a dual electronic-ionic microenvironment to substantially enhance oxygen electrolysis in solid-state batteries. By designing a lithium-decorative catalyst with an engineering crystal structure, the coordinatively unsaturated sites and high concentration of defects alleviate the limitations of electronic-ionic transport in solid interfaces and create a balanced gas-solid microenvironment for solid-state oxygen electrolysis. This strategy facilitates oxygen reduction reaction, mediates the transport of reaction species, and promotes the decomposition of the discharge products, contributing to a high specific capacity with a stable cycling life. Our work provides previously unknown insight into structure-property relationships in solid-state electrolysis for SSLOBs.