context: Our study underlines the importance of gaining deeper insights into the anionic redox activities of Li-rich materials for designing a new cathode material for future LIBs. Promoting the reversible anionic redox contributions while suppressing the irreversible reactions is vital in designing a cathode material with high energy density and good cycling performance. The combined computational/experimental approach presented here can be applied to predict and verify the anionic redox activities in other Li-rich materials to accelerate the discovery of materials with high energy density and good cycling performance.