Low levels of so-called “donor-doping” in titanate-based perovskite oxides such as La for Ba, Sr, and Nb for Ti in (Ba, Sr)TiO3 can significantly reduce the resistivity of these typical (d0) dielectric materials and expand application areas to positive temperature coefficient resistors, thermoelectrics, conductive wafers as thin film substrates, and solid oxide fuel cell anode materials. Here, we show low levels of Nb-doping (≤1 at. %) on the Ti-site in the well-known lead-free piezoelectric perovskite oxide Na0.5Bi0.5TiO3 (NBT) produces completely different behaviours whereby much higher resistivity is obtained, therefore indicating a different donor-doping (substitution) mechanism. There is a switch in conduction mechanism from oxygen-ions in undoped NBT with an activation energy (Ea) of <0.9 eV to electronic (band gap) conduction in 0.5–1 at. % Nb-doped NBT with Ea ∼ 1.5–1.8 eV. This demonstrates the necessity of further systematic doping studies to elucidate the defect chemistry of NBT which is clearly different to that of (Ba,Sr)TiO3. This defect chemistry needs to be understood if NBT-based materials are going to be manufactured on a large scale for commercial applications. This study also illustrates different donor-doping mechanisms to exist within the family of d0 titanate-based perovskites.