Glucose-free and glucose-containing LaCoO(-G), LaSrCoO(-G), and LaCeCoO(-G) perovskite catalysts were synthesizedviathe sol-gel method, over which the oxidation performance of high-concentration CO was investigated. The experimental results indicate that the catalytic activity can be improved by facilely adding glucose during the preparation where glucose creates a reducing atmosphere and takes away the oxygen atoms of perovskites to form more oxygen vacancies and Co. CO self-sustained combustion is favorably achieved and LaCeCoO-G shows the best catalytic performance. Combining the XPS, H-TPR, O-TPD and CO-TPD results, the outstanding performance of LaCeCoO-G is mainly ascribed to the relatively higher concentrations of Co, Ceand oxygen vacancies. The reaction was found to follow the Langmuir-Hinshelwood (L-H) mechanism byin situIR spectroscopy and kinetic results. Furthermore, LaCeCoO-G exhibits good high-temperature durability with unchanged CO conversion of 100% at 760 °C. It is suggested that the addition of glucose and the impregnation of Sr or Ce in perovskites is a feasible strategy to design industrial catalysts for CO self-sustained combustion.