Cost-effective and highly efficient catalyst is a promising way for the removal of CO in automotive exhaust purification. Herein, a series of novel self-assembled CoMn bimetallic catalysts with hollow microcage structure have been prepared through zeolitic imidazole framework (ZIF-67) assisted method followed by direct pyrolysis in static air. Both the Mn loading and the unique hollow microcage structure play important roles in CO low-temperature oxidation, and the highest catalytic activity is obtained for CoMn-2 catalyst, which presents T 100 (temperature of 100 % CO conversion) at 80 °C. Through a systematic series of experiments, we further demonstrate that our catalysts' superior catalytic performance arises from small particle size, high surface active oxygen content and Co 3 + /(Co 2 + + Co 3 + ) ratio. Such configuration of catalysts will pave the way for new strategies to design noblefree high-performance catalysts for CO low-temperature oxidation.