Orbital Hybridization Around the Fermi Level Accelerates Momentary Electric Dipoles in LaCrO₃‐Based Perovskite for Enhanced Electromagnetic Shielding

LaCrO 3 perovskite, with excellent oxidation stability and adjustable energy band structure, exhibits profound potential as electromagnetic shielding materials in high‐temperature, while the low dielectric loss restricts its application. Here, a novel strategy that promoting orbital hybridization around the Fermi level is proposed to induce localized electric dipoles and enhance dielectric loss. The transition metal‐oxygen bond transforms from ionic to weakly metallic after substituting low‐valence Ni 2 ⁺ for half of the Cr 3 ⁺, then the enhanced orbital hybridization between O‐2p and Cr‐3d facilitates electron cloud distortion severely and forms a momentary dipole moment, as evidenced by Born effective charges deviating from the nominal valence by four to six‐fold. As a result, La(Cr 0.5 Ni 0.5 )O 3 demonstrates a giant dielectric loss of ≈180, with polarization relaxation contributing 70–80%. Notably, even after heat treatment at 1000 °C for 20 h, the material maintains exceptional shielding effectiveness of 31 dB. This orbital hybridization strategy promoting electric polarization provides an effective approach to enhance dielectric loss about high‐temperature resistant perovskites, offering valuable guidance for optimizing their shielding performance.