A series of Pr6O11 (x = 0-0.70 mol%)-doped TiO2 ceramics were synthesized by the conventional solid-state reaction method. The microstructure, electrical, and luminescence properties were systematically investigated. The results showed that the as-prepared TiO2 ceramics exhibited strong red emission at 606 nm at room temperature and the optimal photoluminescence were obtained at x = 0.30. In addition, the nonlinear coefficient was improved with the amount of Pr6O11 dopant, reaching the maximum value at x = 0.50. Therefore, Pr6O11-doped TiO2 ceramics, which simultaneously exhibited luminescent properties and good electrical properties, would be useful in novel multifunctional devices.