Nickel-rich layered oxides are currently considered the most practical candidates for realizing high-energy-density lithium metal batteries (LMBs) because of their relatively high capacities. However, undesired nickel-rich cathode-electrolyte interactions hinder their applicability. Here, we report a satisfactory combination of an antioxidant fluorinated ether solvent and an ionic additive that can form a stable, robust interfacial structure on the nickel-rich cathode in ether-based electrolytes. The fluorinated ether 1,1,2,2-tetrafluoroethyl-1H,1H,5H-octafluoropentyl ether (TFOFE) introduced as a cosolvent into ether-based electrolytes stabilizes the electrolytes against oxidation at the LiNi0.8Mn0.1Co0.1O2 (NCM811) cathode while simultaneously preserving the electrochemical performance of the Li metal anode. Lithium difluoro(bisoxalato)phosphate (LiDFBP) forms a uniform cathode-electrolyte interphase that limits the generation of microcracks inside secondary particles and undesired dissolution of transition metal ions such as nickel, cobalt, and manganese from the cathode into the electrolyte. Using TFOFE and LiDFBP in ether-based electrolytes provides an excellent capacity retention of 94.5% in a Li vertical bar NCM811 cell after 100 cycles and enables the delivery of significantly increased capacity at high charge and discharge rates by manipulating the interfaces of both electrodes. This research provides insights into advancing electrolyte technologies to resolve the interfacial instability of nickel-rich cathodes in LMBs.