To reduce the issue of tri-primary color reabsorption, a new approach for single-phase phosphors as light-emitting diodes (LEDs) has been recommended. The structures, morphology, photoluminescence, thermal stability, and luminescence mechanism of a variety of Ca3Bi (PO4)3(CBPO): Ce3+/Dy3+phosphors were investigated. XRD characterization showed that all CBPO samples were eulytite structures. Furthermore, the energy transfer process from Ce3+to Dy3+in CBPO is systematically investigated in this work, and the color of light can be adjusted by changing the ratio of doped ions. Under UV light, energy is transferred from Ce3+-Dy3+mainly through quadrupole-quadrupole interactions in the CBPO host, and doping with different Dy3+concentrations tunes the emission color from blue to white. The thermal stability of the CBPO: 0.04Ce3+, 0.08Dy3+samples is outstanding, and the CIE coordinates of the samples after emission have little effect with temperature, while their emission intensity at 423 K is as strong as that at room temperature, reaching 90%. The above results indicate that this CBPO material has great potential as a white light phosphor under near-UV excitation at the optimized concentration of Ce3+and Dy3+.