A series of white-emitting CaTiO3:Dy3+ and CaTiO3:Dy3+, Li+ phosphors for light-emitting diode applications were prepared by conventional solid-state reactions. The phase of the as-prepared powders were measured by X-ray diffraction pattern. The emission and excitation spectra as well as the luminescence decays were investigated. The excited spectra indicated that they have intense excitation at 353 (6H15/2–6P7/2), 366 (6H15/2–4P5/2), 388 (6H15/2–4I13/2) and 450 nm (6H15/2–4I152). Meanwhile, the emission of Dy3+ ions upon 353 nm excitation was observed at 480 nm (blue) due to the 4F9/2–6H15/2 transitions, 573 nm (yellow) due to 4F9/2–6H13/2 transitions and a weak 665 nm (red) due to 4F9/2–6H11/2 emissions, respectively. As a charge compensator, Li+ ions were incorporated into CaTiO3:Dy3+, which enhanced the PL intensities depending on the doping concentration of Li+. Moreover, the chromaticity coordinates of CaTiO3:Dy3+ and CaTiO3:Dy3+, Li+ were very close to the ideal white light coordinates (0.33, 0.33). All the results demonstrated that CaTiO3:Dy3+ and CaTiO3:Dy3+, Li+ might be potential phosphors for NUV-based white light-emitting diodes.