A series of photoluminescence materials of red-orange-blue three lights emission, Ce/Mn:Cd0.5Zn0.5B4O7 were prepared via a high-temperature solid-state method for the first time. The crystal system, point group and cell parameters of (Cd0.38Ce0.06/ Mn0.03)Zn0.5B4O7 were confirmed by X-ray diffraction. The phosphor belongs to orthorhombic crystal system with Pbca space group. Spectral characteristics of Ce/Mn:Cd0.5Zn0.5B4O7 indicate that excited by 285 nm UV, the emission mainly presents 4T1(4G)→6A1(6S) of Mn2+; excited by 370 nm UV, the emission is mainly 5d→2F5/2, 2F7/2 of Ce3+; excited by 296 nm UV, it shows compound light-emitting of 470 nm and 630 nm with similar emission intensity ratio. Ce3+ and Mn2+ co-exist, and they are the activator and the sensitizer of each other. In the phosphors Ce/MnCd0.5Zn0.5B4O7 there are multiple energy transfers among the host, Ce3+ and Mn2+, which are rarely found. The major energy transfer is Ce3+?Mn2+. Flux CaF2 and KCl can reduce the synthesis temperature and increase the luminous intensity, but they have different effects for Ce3+ and Mn2+ emission spectra