BiFeO3-BaTiO3 is a promising high-temperature lead-free piezo-ceramics due to its high Curie temperature (TC > 500 °C) and excellent piezoelectric properties. However, a high leakage current was often detected in this system, which severely affects its applications. In this work, the 0.7BiFe(1−x)GaxO3-0.3BaTiO3 (BFGax-BT, 0.00 ≤ x ≤ 0.10) system was designed to reveal the reason of leakage-current density decreased by their leakage mechanism. Because of the suppression of generation of Fe2+ and oxygen vacancy (VO∙∙), the leakage mechanism from space charge limited conduction mechanism found in Ga-free BF-BT ceramics turns into Ohmic conduction and Schottky emission mechanism as Fe3+ was replaced with Ga3+. A good combination of piezoelectric properties (d33 = 174 pC N−1 and kp = 29%) and high Curie temperature (TC = 497 °C) was achieved in the BFGa0.06-BT ceramic owning the lowest leakage-current density. This work will provide the clues for preparing the high insulation and high piezoelectric performance BF-BT-based ceramics by suppressing the valence change of Fe3+ and VO∙∙ appearance.