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In order to meet the urgent need for high temperature piezoelectric materials with a Curie temperature over 400 °C, the Mn/Nb co-doped strategy has been proposed to improve the weak piezoelectric performance of the Aurivillius-type Na_0.5Bi_4.5Ti₄O₁₅ (NBT) high temperature piezoelectric ceramics. In this paper, the crystal structure, electrical properties, and thermal stability of the B-site Mn/Nb co-doped Na_0.5Bi_4.5Ti_4-x(Mn_1/3Nb_2/3)<i>_x</i>O₁₅ (NBT-100<i>x</i>) ceramics were systematically investigated by the conventional solid-state reaction method. The crystal structural analysis results indicate that the NBT-100<i>x</i> ceramics have typical bismuth oxide layer type phase structure and high anisotropic plate-like morphology. The lattice parameters and the grain sizes increase with the <i>B</i>-site Mn/Nb co-doped content. The electrical properties were significantly improved by Mn/Nb co-doped modifications. The maximum of the piezoelectric coefficient d₃₃ was found to be 29 pC/N for the NBT-2 ceramics, nearly twice that of the unmodified NBT ceramics. The highest values of the planar electromechanical coupling factor k_p and thickness electromechanical coupling factor k_t were also obtained for the NBT-2 ceramics, at 5.4% and 31.2%, respectively. The dielectric spectroscopy showed that the Curie temperature Tc of the Mn/Nb co-doped NBT-100<i>x</i> ceramics is slightly higher than that of unmodified NBT ceramics (646 °C). The DC resistivity of the NBT-2 ceramics is higher than 10⁶ Ω∙cm at 500 °C. All the results together with the good thermal stability demonstrated the Mn/Nb co-doped ceramics as an effective method to improve the NBT based piezoelectric ceramics and the potential candidates of the Mn/Nb co-doped NBT-100<i>x</i> ceramics for high temperature piezoelectric applications.