AbstractThe effects of donor dopants and acceptor dopants (A and B sites) on the resistivity of CaBi2Nb2O9 (CBN) ceramics were studied. The results indicate that the dominant conduction mechanism of pure CBN is p‐type. When the donor doping amount x < 0.05 on A site and x < 0.02 on B site, the resistivity increased with increasing donor doping. With a further increase of donor doping, the resistivity decreased since conductivity mechanism changes from p‐type to n‐type. The resistivity with acceptor doping is decreased at low temperature and equal to the pure CBN ceramic at high temperature since the resistivity of the grain boundary decreases. This work provides a way to obtain high‐resistivity CBN ceramics by appropriate donor doping, which is benefit for use in high‐temperature piezoelectrics.