The LaMnO, LaCeMnO and LaSrMnO catalysts are synthesized using sugar agent, and the CO self-sustained combustion is investigated, where the catalytic performance is decided by temperature with CO conversions of 10% (T), 50% (T), and 90% (T). The results show that self-sustaining combustion is successfully realized on the catalyst, and the order of activity decrease is as follows: LaCeMnO (with sugar) > LaSrMnO (with sugar) > LaMnO (with sugar) > LaMnO (without sugar) > LaSrMnO (without sugar) > LaCeMnO (without sugar). Combined with the results of XPS, H-TPR, O-TPD and CO-TPD techniques, the excellent activity of LaCeMnO (with sugar) can be attributed to the high content of Mn ions and reactive oxygen vacancies enriched on the catalyst surface, sound low-temperature reduction, and uniform dispersion. Besides, in situ IR spectroscopy results indicate that the catalytic combustion of CO over manganese-based perovskite catalysts follows the L-H mechanism: the chemisorption of CO and O takes place to produce monodentate carbonates and bicarbonate species, which then decompose to yield CO release. The high-temperature stability test provides evidence that the LaCeMnO (with sugar) gives 100% CO conversion and that the activities remain almost unchanged after reaction for 12 h, where the temperature of catalyst bed reaches about 717 °C. The results obtained are helpful to accept this technology on efficient and clean energy utilization in iron and steel industry.