<p>BiFeO₃ (BFO) as a promising lead-free ferroelectric material has attracted significant attention due to its unique electrical properties and potential applications in sensors and memory devices. However, the high leakage current and difficulty in obtaining a pure phase for BFO ceramics still significantly limit its practical application. Herein, the introduction of Pr³⁺ at the A sites and the rapid quenching are synergistically applied to achieve the single-phase Bi_1−<i>x</i>Pr_<i>x</i>FeO₃ ceramics and improve its electrical properties. The effects of Pr³⁺ on the microstructure, dielectric properties, and ferroelectric properties of Bi_1−<i>x</i>Pr_<i>x</i>FeO₃ ceramics were systematically studied. The results show that the Bi_1−<i>x</i>Pr_<i>x</i>FeO₃ (<i>x</i> = 0–0.075) ceramics prepared by the rapid quenching method are primarily rhombohedral phases, and the introduction of Pr³⁺ significantly inhibits the formation of impurity phase. The partial substitution of more stable Pr³⁺ for Bi³⁺ not only refines the grain size of Bi_1−<i>x</i>Pr_<i>x</i>FeO₃ ceramics but also significantly reduces their leakage current density. Moreover, the introduction of Pr³⁺ also lead to the increased remnant polarization of BiFeO₃ ceramics. The synergistic effect of rapid quenching and Pr³⁺ doping plays a critical role in improving the electrical properties of BiFeO₃ ceramics.</p>