The utilization of Lithium-rich materials (LR) with oxygen anionic redox (OAR) activity as cathode materials in Li metal batteries has gradually emerged as a prevailing trend in designing high-specific energy batteries. However, the interface design of LR and its influence mechanism on anionic redox chemistry are still ambiguous. Herein, in-situ interface engineering with an LiF-rich cathode-electrolyte interface (CEI) using all-fluorinated electrolyte was proposed and the role of the CEI on OAR was clarified. The shielding effect on high-valence oxygen ions is revealed that the dense, uniform, thin, and robust LiF-rich CEI protects high-valence oxygen ions from the electrolyte, inhibits electrolyte decomposition and interface thickening, and ameliorates structural degradation and oxygen loss of LR. And a more critical effect of CEI on the OAR process is demonstrated that the LiF-rich CEI layer prevents molecular oxygen in the bulk from escaping into the electrolyte as O2 gas and makes the oxidized oxygen exists more in the form of peroxo-like oxygen dimer O2n−. Besides the stabilization of OAR in the cathode side, the all-fluorinated electrolyte along with its enhancement in the Li anode enable high safety, excellent cycling stability, and fast charging performance for high energy lithium metal batteries.