BiFeO₃–BaTiO₃ (BF–BT) based piezoelectric ceramics are a kind of high-temperature lead-free piezoelectric ceramics with great development prospects due to their high Curie temperature (T_C) and excellent electrical properties. However, large leakage current limits their performance improvement and practical applications. In this work, direct current (DC) test, alternating current (AC) impedance, and Hall tests were used to investigate conduction mechanisms of 0.75BiFeO₃–0.25BaTiO₃ ceramics over a wide temperature range. In the range of room temperature (RT)−150 ℃, ohmic conduction plays a predominant effect, and the main carriers are p-type holes with the activation energy (E_a) of 0.51 eV. When T > 200 ℃, the E_a value calculated from the AC impedance and Hall data is 1.03 eV with oxygen vacancies as a cause of high conductivity. The diffusion behavior of thermally activated oxygen vacancies is affected by crystal symmetry, oxygen vacancy concentration, and distribution, dominating internal conduction mechanism. Deciphering the conduction mechanisms over the three temperature ranges would pave the way for further improving the insulation and electrical properties of BiFeO₃–BaTiO₃ ceramics.