LiCO2 battery is a very promising power source with high energy density. Its performance is strongly restricted by the cathode catalysts, in which carbon-based catalysts have been mostly investigated up to now. However, the impacting factors on the performance of carbon catalysts is not yet elucidated. Here, we employed a variety of carbon materials with different pore-structure features as the cathode catalysts of LiCO2 batteries to reveal which are the main influencing factor on the catalytic performance of carbon catalysts. It is found that suitable pore shape (most important), large pore size and high surface area are crucial factors to the catalytic performance of carbon catalysts. This finding is of great significance to the further development of LiCO2 batteries.