Selective catalytic oxidation of cyclohexane into cyclohexanol and cyclohexanone (KA oil) is an important but challenging reaction in the modern chemistry industry, which is characterized by a low KA oil selectivity under high conversion of cyclohexane. To solve the contradictory issue between cyclohexane conversion and KA oil selectivity, A-site-doped Co-based perovskite oxides (La1–xAxCoO3, A = Mg, Ca, Sr, and Ba) as catalysts are used for solvent-free cyclohexane oxidation using molecular oxygen as an oxidant. Among all selected perovskite catalysts, Ca element-modified La0.5Ca0.5CoO3exhibits the best catalytic performance with a cyclohexane conversion of 7.7% and a KA oil selectivity of 86.5% under optimal reaction conditions. The characterization results show that doping the Ca element into the A-site can effectively regulate the surface properties of LaCoO3by changing the molar ratio of Co2+/Co3+ions, creating more oxygen vacancies, and altering the acidity and basicity, which play essential roles in promoting the activation of O2and the reduction/decomposition of cyclohexyl hydroperoxide (CHHP). This work demonstrates that the catalytic performance of LaCoO3in the aerobic oxidation of cyclohexane can be further modified by optimizing its A-site compositions, which opens a large space for the design of highly active and selective perovskite-type catalysts for partial oxidation of saturated alkanes.