Novel single-phased and emission-tunable layered Bi4Ti3O12:Pr3+ nanosheets have been successfully synthesized via molten salt method. The as-prepared samples were characterized by X-ray diffraction and scanning electron microscopy to investigate their crystalline phases and morphologies. Furthermore, we explored the photoluminescence properties of the Bi4Ti3O12:Pr3+ phosphors, while the cross-relaxation processes between 1D2, 3P0 emitting states and the Pr3+–Ti4+ intervalence charge transfer state, color tuning and thermally stability were discussed in detail. Besides, the emission hue of Bi4Ti3O12:Pr3+ could be adjusted from white-light (0.3059, 0.2731) to yellow (0.5167, 0.4792) by tuning the excitation wavelength, in which the ratio of 3P0→3H4 and 1D2→3H4 was changed. In addition, the increases in temperatures led to the cooperative effects of thermal-quenching behavior and the cross-relaxation processes, thus resulting in the significant decrease of 3P0→3H4 emission in comparison to the 1D2→3H4 emission. The results suggested that the Bi4Ti3O12:Pr3+ is an effective color-tuning phosphor.