Lithium metal batteries (LMBs) integrating high-voltage nickel-rich cathodes are promising candidates for energy densities exceeding 500 Wh kg−1. However, their practical development is hindered by severe interfacial reactivity at both electrodes, which imposes stringent requirements on electrolyte design. A fundamental challenge lies in the insufficient understanding of interactions among electrolyte components and their potential synergistic effects, which restricts precise regulation of solvation structures and simultaneous stabilization of dual interfaces. Herein, we propose a molecular orchestration strategy based on complementary molecular charge engineering to induce mutual reinforcement among electrolyte constituents. Functional molecular pairs with complementary charge demands are rationally integrated through cooperative intermolecular association, serving as synergistic precursors. The resulting intermolecular charge transfer modulates Li+ coordination affinity and enhances the reductive and oxidative reactivity of each additive, enabling synchronous dual-interface optimization. Consequently, the electrolyte supports ultrahigh voltage operation (4.6 V), fast charging (10C), a wide temperature (−25 to 50 °C) and long-term stability over 3200 h. Notably, a high energy density exceeding 513 Wh kg−1 (based on the total cell weight) is attained in 5.4 Ah Li‖NCM811 pouch cells under harsh practical conditions. Departing from conventional reliance on high-concentration electrolytes or increased additive dosages, this work establishes a practical electrolyte-engineering paradigm centered on the systematic organization and activation of latent functionalities, providing an energetic perspective for high-performance LMBs.