White light solid-state lighting applications still face significant challenges due to insufficient efficient and stable red light emitting materials. Therefore, a series of orange-red fluorescent materials, CaLu2-xMg2Si3O12:xCe3+ (CLMS:xCe3+; x = 0.02, 0.04, 0.06, 0.08, 0.10, 0.12) were prepared in this paper. Luminescence spectra testing revealed that the optimal concentration of Ce3+ ions in the crystal lattice is x = 0.04. At 460 nm excitation, the emission wavelength is approximately 592 nm. To enhance the thermal stability and luminescence performance of CLMS:Ce3+, the CaLu1.96-yMeyMg2Si3O12:0.04Ce3+ (Me = Sr, Ba; y = 0, 0.02, 0.05, 0.10, 0.15, 0.20) fluorescent materials were successfully prepared. It was found that phosphor's fluorescence intensity was enhanced after the introduction of Sr2+ or Ba2+ ions. Meanwhile, the phosphors were tested for thermal stability, and the emission intensities of CLMS:0.04Ce3+, CLMS:0.04Ce3+,0.10Sr2+, and CLMS:0.04Ce3+,0.05Ba2+ phosphors decreased to 77.60%, 85.53%, and 87.63% at 423 K, respectively. This proves that Sr2+ and Ba2+ ions have a positive effect on the thermal stability performance of CLMS:0.04Ce3+ phosphor. Testing of the w-LED devices, the CCT was reduced. The CRI was improved to 80.4 and 81.6 and luminescence efficiency was improved to 107.71 lm/W and 115.04 lm/W after Sr2+ or Ba2+ ions were introduced. In summary, this study demonstrates that CaLu2-x-yMeyMg2Si3O12:xCe3+ (Me = Sr, Ba) is an auspicious fluorescent material with high thermal stability, which is potentially informative for the field of white-light illumination.