The photoluminescence and low-voltage cathodoluminescence characteristics of BaTi4O9:Pr3+ were investigated. The excitation band of intervalence charge transfer (IVCT) of BaTi4O9:Pr3+ emerged distinctly at 330 nm. The resultant emissions appeared at 606–643 nm corresponding to the 1D2→3H4 transition. In BaTi4O9:Pr3+, the emission of 3P0→3H4 transition at 490 nm was not observed. The results were in a pure red color emission.