This paper investigates the photoluminescence properties of NaCaTiNbO6:Pr^3+ and NaCaTiNbO6:Pr^3+,Bi^3+ phosphors. NaCaTiNbO6:Pr^3+ and NaCaTiNbO6:Pr^3+,Bi^3+ powder were synthesized successfully by solid state reaction method. Phase purity was checked using X-ray powder diffractometry(XRD). The excitation and emission spectra were recorded to elucidate the photoluminescence properties of NaCaTiNbO6:Pr^3+ and NaCaTiNbO6:Pr^3+,Bi^3+. Furthermore,fluorescence lifetime measurements were performed. The excitation spectra of NaCaTiNbO6:Pr^3+ show a main band centered at around 357 nm.The luminescence spectra of NaCaTiNbO6:Pr^3+ exhibit a red emission peak at 615 nm from the ^1 D2→^3 H4 transition of Pr^3+ ions. With the introduction of the Bi^3+ ion into NaCaTiNbO6:Pr^3+, the luminescence intensity is enhanced nearly two times. Meanwhile,the absorption band edge of NaCaTiNbO6:Pr^3+ is shifted from 380 to 420 nm. Thus, this study shows that the red phosphor NaCaTiNbO6:Pr^3+ incorporated with Bi^3+ is advantageous for light-emitting diode applications.