New piezoelectric ceramics, 0.71BiFe1−x(Ni1/2Ti1/2)xO3−0.29BaTiO3+0.6 wt% MnO2 [BFNTx–BT] (x = 0–0.09), were fabricated using conventional mixed‐oxide method. It was found that the introduction of BNT into BF‐BT system caused insignificant change in crystal structure, which is a single‐phase perovskite structure. However, an obvious variation in microstructure took place. The ceramics with composition of x = 0.03 showed enhanced piezoelectric, electromechanical, and ferroelectric properties with piezoelectric constant d33 = 156 pC/N, planar electromechanical coupling factors kp = 0.308, remnant polarization Pr = 22.5 μC/cm2, and coercive field Ec = 28.2 kV/cm, with a high Curie temperature Tc = 431°C, respectively. The combination of good piezoelectric properties and high Tc makes these ceramics suitable for elevated temperature piezoelectric devices.