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The effect mechanism of lattice distortion caused by heterovalent rare‐earth and alkaline‐earth ions co‐doping in the electrical properties of piezo‐ceramics is generally concerning. Herein, the Sm2O3/MgO co‐doped 0.65(Ba0.96Sr0.04TiO3)–0.35(Bi0.50Na0.50TiO3) (BST–BNT: x(Sm, Mg)) (0 ≤ x ≤ 0.25 wt%) ceramics are prepared by Pechini sol–gel method. The reversibility transition from the tetragonal P4/mmm...