The excessive use of fossil fuels has led to increasing concerns about global climate change and national energy storage. It is urgent to develop some clean, efficient, and reliable technologies to harvest and store the clean energy generated from solar and wind. Electrochemical energy technology such as batteries and fuel cells can serve as an ideal medium to store and release electricity. Among various electrochemical systems, Li-air battery has attracted wide attention to be a promising next-generation energy storage device due to its high theoretical capacity (11,000 Wh/kg). Thus, one of the most important topics is to develop an efficient, economical and safe Li-air battery. Here, we develop a series of Co-doped metal-organic frameworks derived carbon catalysts (Co-MOFs) of different sizes, which can be employed as the high-performance bifunctional cathode catalysts for Li-air battery. Controlled by anion type and the amount of 1-methyl imidazole, Co-MOFs catalysts can be obtained with various sizes, ranging from 50 nm to 5 µm. Further optimization of the Co content and thermal activation procedure can produce a highly active Co-N-C catalyst, showing a half-wave potential of 0.818 V vs. RHE in aqueous solution and high selectivity for four-electron reduction, mainly due to the influence of the final morphology and structure including surface area, pore structure and nitrogen doping. Co-N-C catalyst also exhibits a higher performance in terms of onset potential, half-wave potential and current density in non-aqueous solution when compared with non-metal-MOFs derived catalysts. The high oxygen reduction reaction (ORR) activity of this catalyst could be attributed to the Co-N_x active sites embedded in the porous carbon matrix. In the battery, the cathode consisting of Co-MOFs catalysts shows a high discharged capacity of 13,000 mAh/g and a relative stable cycling performance up to 50 cycles, which implies that Co-MOFs catalysts could be a promising candidate as the replacement of platinum group metal catalysts for Li-air battery applications.