Antiferrodistortive Matrix Engineering Reprograms Polarization Pathways for Ultrahigh Energy Storage at Moderate Electric Fields

ABSTRACT Relaxor ferroelectrics (RFEs) are promising dielectric materials for pulsed multilayer ceramic capacitors because of their rapid polarization response. However, under practical electric fields, polarization rapidly approaches saturation as polar nanoregions exhaust their nonlinear switching capability, fundamentally limiting energy‐storage performance. Here we demonstrate that antiferrodistortive matrix engineering reprograms the polarization evolution pathway through a polarization dormancy–awakening process. Long‐range antiferrodistortive modulation, introduced by the intrinsic lattice instability of CaZrO 3 in a (Bi 0.5 Na 0.4 K 0.1 )TiO 3 matrix, creates local strain fields that temporarily suppress PNR switching and progressively awaken dormant polarization under moderate electric fields. This substantially extends the nonlinear polarization‐response regime without inducing ferroelectric or antiferroelectric ordering. Atomic‐resolution electron microscopy, electron diffraction, and phase‐field simulations collectively reveal the structural origin of the awakening behavior and its coupling to local polarization dynamics. Consequently, the engineered relaxor ceramic achieves an ultrahigh recoverable energy‐storage density of 12.3 J cm – 3 with an energy‐storage efficiency of 87.4% at 520 kV cm – 1 , representing a benchmark performance for bulk RFE ceramics operating under moderate electric fields. This work establishes antiferrodistortive matrix engineering as a promising design strategy for reprogramming polarization evolution in RFEs toward high‐performance dielectric energy storage.