(1–x)BiFeO₃–xBaTiO₃(BF–xBT, x=0.28,0.29,0.30,0.31) piezoelectric ceramics were prepared by a conventional sintering technology. The relationship between the phase structure and dielectric, ferroelectric and piezoelectric properties of the ceramics near the phase boundary was investigated. Based on the results by X-ray diffraction, all the samples present a pure perovskite phase structure without any impurity phase, and all the ceramics are located around the rhombohedral–pseudocubic phase boundary. The phase structure gradually transforms from rhombohedral to pseudocubic phase as x increases, and the content of R and pC phase tends to be equal when x=0.30, showing the optimum electrical properties (i.e., piezoelectric coefficient (d₃₃) =165 pC/N, remanent polarization (P_r) = 26.80 μC/cm₂, and the Curie temperature (T_C) = 465 ℃). In addition, the changes of Raman vibration mode and diffuseness factor of the samples after quenching indicate that the quenching process can effectively improve the long range order degree and the temperature stability of ferroelectric phase of the samples, resulting in a further increase in the Curie temperature of BF–xBT ceramics. For a ceramic BF–0.30BT, the enhanced dielectric and ferroelectric properties are obtained due to its more proper R/pC phase ratio and quenching process. Also, the relationship between the phase structure evolution and piezoelectric properties of BF–xBT ceramics was revealed, and the electrical properties of BF–xBT ceramics were further optimized by quenching process, so as to provide a reference for broadening the application temperature range of the BF–BT system materials.