The red-emitting phosphors of CaBi2Ta2O9: Eu3+ and CaBi2Ta2O9: Eu3+/La3+ were prepared by the high-temperature solid-state reaction method. By using X-ray diffraction, the structural properties of powders have been analyzed. The photoluminescence excitation and emission spectra of CaBi2Ta2O9: Eu3+, and the dependence of luminescence intensity on doped Eu3+ ions concentration were investigated. The results show that CaBi2Ta2O9: Eu3+ can be efficiently excited by near-UV and blue light to realize an intense red luminescence (615 nm) corresponding to the electric dipole transition 5D0 arrow right 7F2 of Eu3+ ions. Meantime, an enhancement of photoluminescence intensity was observed in La3+ ions doped CaBi2Ta2O9: Eu3+ phosphors. The CIE chromaticity coordinates of CaBi2Ta2O9: Eu3+ and CaBi2Ta2O9: Eu3+/La3+ are (0.6121, 0.3835) and (0.6141, 0.3821), corresponding to the hues of orange-red. The phosphors can be suggested to be a potential red-emitting phosphor for the application on white LEDs under irradiation of near-UV or blue chips.