Multi‐Polar Order Engineering Enables Near‐Ideal Efficiency in Lead‐Free Energy Storage Perovskite

Abstract Toxic lead‐based dielectrics dominate high‐performance capacitors, creating urgent environmental and supply‐chain challenges. Multi‐polar order engineering is deployed to create an industrially scalable lead‐free perovskite achieving simultaneous record efficiency (η ≈ 95%) and energy density (12 J cm −3 ). Phase‐field simulations are also used to guide micro‐to‐nano domain design to construct switchable polar nano region that delay polarization saturation. Crucially, sub‐angstrom electronic state optimization – previously unexplored in energy storage dielectrics – is revealed as pivotal: synchrotron XAS quantifies Nb‐O dipole ionicity enhancement via electronic polarization, while atomic‐resolution electron microscopy statistically confirms bond‐length homogenization and distortion reduction that structurally anchor this effect. This hierarchical atomic‐to‐electronic control reshapes the electrical microstructure, enabling unified charge dynamics (validated by DRT analysis) that deliver ultrafast field response (<32 ns discharge) and exceptional thermal resilience (< ±4% current fluctuation, 25–150 °C). Fabricated from commodity precursors, the material eliminates the reliance on rare‐earth precursors that are common in PLZT production, significantly lowering costs while mitigating environmental impacts. Overall, this work establishes a sustainable pathway for grid‐scale power electronics.