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Abstract High‐voltage lithium metal batteries with nickel‐rich oxide cathodes (LiNi_0.8Co_0.1Mn_0.1O₂, NCM811) represent one of the most promising approaches to achieve high energy density up to 500 Wh kg⁻¹. However, severe interfacial side reactions occur at both NCM811 cathode and lithium anode at ultrahigh voltages (>4.6 V). To address these issues, various electrolytes have been developed, but they still suffer from electrolyte decomposition, leading to moderate voltages and insufficient cycling. Herein, we introduce (3,3,3‐trifluoropropyl)trimethoxy silane (TTMS) as an asymmetrically fluorinated single solvent, which incorporates both strongly solvating (─OCH₃) and weakly solvating (─CF₃) groups. The designed 2.1 mol L⁻¹(M) LiFSI/TTMS electrolyte achieves excellent compatibility with both NCM811 cathode and Li metal anode due to its unique anion‐dominating solvation structures and inorganic‐rich interphase formation. Consequently, it enables stable cycling in the Li||NCM811 battery at an ultrahigh voltage of 4.8 V, with 84.5% capacity retention after 300 cycles. Even under more aggressive conditions, including high temperature (60 °C) and anode‐less configuration (N/P ratio = 1.76), the Li||NCM811 battery exhibits remarkable capacity retention (>80%) over 300 cycles. This work underscores the effectiveness of electrolyte engineering for developing ultrahigh‐voltage and long‐cycling battery systems.