BaY1.94-xAl4SiO12:0.06Ce3+, xPr3+ (x = 0, 0.01, 0.02, 0.03 and 0.04) phosphors were successfully prepared via the solid-state synthesis method at 1450°C. The diffuse reflection spectra, emission spectra, thermal luminescence stability of the phosphors and the optical properties of the white LEDs fabricated by employing the phosphors were investigated. BaY1.94-xAl4SiO12:0.06Ce3+, xPr3+ phosphors can be effectively excited by blue light. Excited by 450 nm, the emission intensity located at 613 nm of BaY1.94-xAl4SiO12:0.06Ce3+, xPr3+ phosphor significantly increases as the Pr3+ concentration increases, and the maximum intensity is reached at x = 0.02, but the luminescence intensity located at 540 nm of BaY1.94-xAl4SiO12:0.06Ce3+, xPr3+ phosphor decreases as the concentration of Pr3+ increases. The Ra value of the white LED fabricated by employing BaY1.92Al4SiO12:0.06Ce3+, 0.02Pr3+ as yellow phosphor was better than that of the white LED made by using BaY1.94Al4SiO12:0.06Ce3+. All the experimental results demonstrate that the red region of the emission spectrum of BaY1.94Al4SiO12:0.06Ce3+ phosphor could be effectively improved by co-doping Pr3+, however, the emission intensity and thermal quenching performance will be slightly weakened.