Ca0.6(Li0.5Bi0.5‐xPrx)0.4Bi2Nb2O9 ceramics were prepared via a solid‐state reaction method. The effect of the Pr content on the structural and electrical properties was systematically investigated. X‐ray diffraction (XRD) combined with Rietveld refinement and X‐ray photoelectron spectroscopy (XPS) demonstrated that a moderate amount of Pr3+ can be incorporated into the NbO6 octahedra, while excess Pr3+ ions probably enter into the (Bi2O2)2+ layers, thus resulting in an increase in the tetragonality of the crystal structure. The introduction of Pr suppressed the generation of oxygen vacancies and improved the preferential grain growth along the c‐axis, which might be responsible for enhancing the resistivity (ρ ~ 106 Ω cm at 600°C). The replacement of Pr3+ for A‐site Bi3+ enhanced the piezoelectric property, and the piezoelectric constant d33 increased from 13.8 pC/N to 16.3 pC/N. The high depolarization temperature (up to 900°C) implied that CBN‐LBP100x ceramics are promising candidates for ultrahigh‐temperature application.