AbstractBiFeO3–SrTiO3 (BF–ST) ceramics have been considered a novel class of lead‐free dielectric materials exhibiting notable dielectric constants and remarkable thermal stability. In this work, we fabricated a series of (1 − x)BF–xST (0.32 ≤ x ≤ 0.44) ceramics near the morphotropic phase boundary and comprehensively investigated their microstructure and electrical properties, which seeks to optimize the piezoelectric performance. As the ST content increases, a gradual reduction in the rhombohedral phase fraction is observed alongside a corresponding increase in the cubic phase fraction. Although x = 0.38, the maximum grain size of 5.66 μm is obtained, accompanied by a distinctive heterogeneous core–shell microstructure, which demonstrates a high remanent polarization of 51.2 μC/cm2 and a maximum d33 value of 72 pC/N. Furthermore, impedance spectroscopy analysis reveals the formation of a conductive core and a nonconductive shell within the sample. These findings highlight the potential of optimized BF–ST ceramics as promising alternatives to lead‐based piezoelectric materials, offering exceptional ferroelectric and piezoelectric properties.