Abstract The intrinsic conduction mechanism and optimal sintering atmosphere of (Ba 0.85 Ca 0.15 )(Zr 0.1 Ti 0.9 )O 3 (BCZT) ceramics were regulated by Mn-doping element in this work. By Hall and impedance analysis, the undoped BCZT ceramics exhibit a typical n-type conduction mechanism, and the electron concentration decreases with the increasing oxygen partial pressure. Therefore, the undoped ceramics exhibit best electrical properties (piezoelectrical constant d 33 = 585 pC·N −1 , electro-mechanical coupling factor k p = 56%) in O 2 . A handful of Mn-doping element would transfer the conduction mechanism from n-type into p-type. And the hole concentration reduces with the decreasing oxygen partial pressure for Mn-doped BCZT ceramics. Therefore, the Mn-doped ceramics sintered in N2 have the highest insulation resistance and best piezoelectric properties ( d 33 = 505 pC·N −1 , k p = 50%). The experimental results demonstrate that the Mn-doping element can effectively adjust the intrinsic conduction mechanism and then predict the optimal atmosphere.