The design of cathode/electrolyte interfaces in high-energy density Li-ion batteries is critical to protect the surface against undesirable oxygen release from the cathodes when batteries are charged to high voltage. However, the involvement of the engineered interface in the cationic and anionic redox reactions associated with (de-)lithiation is often ignored, mostly due to the difficulty to separate these processes from chemical/catalytic reactions at the cathode/electrolyte interface. Here, a new electron energy band diagrams concept is developed that includes the examination of the electrochemical- and ionization- potentials evolution upon batteries cycling. The approach enables to forecast the intrinsic stability of the cathodes and discriminate the reaction pathways associated with interfacial electronic charge-transfer mechanisms. Specifically, light is shed on the evolution of cationic and anionic redox in high-energy density lithium-rich 0.33Li