This study investigates the effect of poling electric field on polarization alignment, dielectric dispersion, relaxor feature, phase transition temperature (Tm), and piezoelectric properties evolution of (1–x)BiFeO3–xBaTiO3[(1–x)BF–xBT] ceramics with x = 0.26, 0.29, 0.32, and 0.35. The XRD pattern studies indicate that the application electric field induced the polarization alignment along with a significant change of the diffraction intensity of peaks, which gives rise to increasing piezoelectric properties. Simultaneously, the degree of dielectric dispersion and diffuse factor γ in the modified Curie–Weiss equation and Tm increase after applying the poling electric field. Moreover, the relaxor characteristics are more evident with increasing BT content. The dielectric behavior and relaxor feature may be attributed to the small random field domains resulting from local charge imbalance due to off‐valent substituents between A‐ and B‐site cation in (1–x)BF–xBT ceramics. Meanwhile, the application of the poling electric field probably increases the strength of the neighboring dipole–dipole interaction, giving the enhanced degree of dielectric dispersion and Tm.