Lithium carbon dioxide (Li–CO2) batteries, noted for their high discharge voltage of approximately 2.8 V and substantial theoretical specific energy of 1876 Wh kg−1, represent a promising avenue for new energy sources and CO2 emission reduction. However, the practical application of these batteries faces significant hurdles, particularly at high current densities and over extended cycle lives, due to their complex reaction mechanisms and slow kinetics. This paper delves into the recent advancements in cathode catalysts for Li–CO2 batteries, with a specific focus on the designing philosophy from composition, geometry, and homogeneity of the catalysts to the proper test conditions and real‐world application. It surveys the possible catalytic mechanisms, giving readers a brief introduction of how the energy is stored and released as well as the critical exploration of the relationship between material properties and performances. Specifically, optimization and standardization of test conditions for Li–CO2 battery research is highlighted to enhance data comparability, which is also critical to facilitate the practical application of Li–CO2 batteries. This review aims to bring up inspiration from previous work to advance the design of more effective and sustainable cathode catalysts, tailored to meet the practical demands of Li–CO2 batteries.