Lead-free sodium–bismuth titanate (Na0.5Bi0.5TiO3, NBT) nanoceramics synthesized by sol–gel method were doped with CeO2 by using solid-state method from 0.0 to 5.0 wt%. The effects of CeO2-doped NBT on structure and microstructure as well as electrical properties were investigated. X-ray analysis shows that CeO2 diffuses into the lattice of NBT to form a solid solution and form morphotropic phase boundary between rhombohedral and tetragonal phase structure in NBT during the sintering process. The electrical properties of NBT ceramics have been greatly improved by doping certain amount of CeO2. The NBT-0.6 wt% CeO2 shows improvement in dielectric properties at room temperature with the highest dielectric constant at 10 kHz (em′ = 1276, tan δ = 0.03 and Tm = 370 °C), high remanent polarization (Pr = 56 μC cm−2) and low coercive field (Ec = 53 kV cm−1). Piezoelectric properties were enhanced with the doping, where the piezoelectric constant d33 = 90 pC N−1 and enhance in mechanical coupling factor k33 = 0.44. The results suggest that the NBT-0.6 CeO2 ceramics can be a suitable material for sensor, actuator or memory device application.