Due to the obvious advantage in potassium reserves, potassium‐ion batteries (PIBs) are now receiving increasing research attention as an alternative energy storage system for lithium‐ion batteries (LIBs). Unfortunately, the large size of K+ makes it a challenging task to identify suitable electrode materials, particularly cathode ones that determine the energy density of PIBs, capable of tolerating the serious structural deformation during the continuous intercalation/deintercalation of K+. It is therefore of paramount importance that proper design principles of cathode materials be followed to ensure stable electrochemical performance if a practical application of PIBs is expected. Herein, the current knowledge on the structural engineering of cathode materials acquired during the battle against its performance degradation is summarized. The K+ storage behavior of different types of cathodes is discussed in detail and the structure–performance relationship of materials sensitive to their different lattice frameworks is highlighted. The key issues facing the future development of different categories of cathode materials are also highlighted and perspectives for potential approaches and strategies to promote the further development of PIBs are provided. Potassium‐ion batteries (PIBs) are now receiving increasing research attention due to their obvious advantage regarding the potassium reserves. Cathode materials, which determine the energy density of PIBs, usually suffer from serious structural deformation during continuous K+ (de)intercalation. Therefore, proper structural‐design principles of cathode materials should be focused on to ensure high performance to promote the further development of PIBs.