Sodium‐ion batteries are promising for sustainable energy storage, but their energy density still lags behind lithium‐ion systems. Na ₃ V ₂ (PO ₄ ) ₂ F ₃ (NVPF) is an attractive high‐voltage polyanionic cathode, but fluorine loss generates low‐voltage Na ₃ V ₂ (PO ₄ ) ₃ impurities that lower energy density and aggravate lattice deformation during cycling. Here, we report a multielement V‐site charge modulation strategy, realized in Na _3‐δ V _1.9 Zr _0.02 Ti _0.02 Cr _0.02 Fe _0.02 Al _0.02 (PO ₄ ) ₂ F ₃ (ME‐NVPF). The deliberate combination of high‐valence Zr ⁴⁺ , Ti ⁴⁺ , and same‐valence Cr ³⁺ , Fe ³⁺ , Al ³⁺ cations creates a heterogeneous M–O/F bonding network with multi‐directional electrostatic interactions enhancing lattice‐F retention that completely eliminates NVP impurities, lowers the Na ⁺ migration barrier, and reduces unit‐cell volume variation to merely 2.87%. Consequently, ME‐NVPF delivers a record‐high energy density of 477 Wh kg ⁻¹ , sustains 11 000 cycles, operates across −40 to 80°C, and is further validated in 600 mAh‐level pouch cells. This work establishes multielement compositional regulation as an effective strategy for designing high‐energy, long‐life, and all‐temperature polyanionic cathodes.

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