The electrical properties of B-site donor and acceptor doped Aurivillius phase Bi3NbTiO9-based ceramics have been investigated. The effect of donor and acceptor doping on the dielectric constant, coercive field, dc conductivity and piezoelectric constant are presented. The band gap of Bi3NbTiO9 (BNTO) is about 3.4 ± 0.2 eV, determined from high-temperature dc conductivity measurements. All of the ceramics are ferroelectrics with high Curie points (~900 °C). In acceptor doped ceramics, a low-temperature peak in the dielectric loss tangent is explained in terms of a Debye-type relaxation that results from an oxygen ion-jump mechanism. The activation energy for the relaxation is calculated as 0.93 ± 0.05 eV. The reduction of the piezoelectric constant below 500 °C is produced by depolarization, which is produced by the switching of thermally unstable non-180° domain walls.