Single-phase Ca19Zn2(PO4)14:Ce3+,Tb3+,Mn2+ phosphors have been prepared by a high temperature solid-state reaction method. X-ray diffraction (XRD), scanning electric microscopy (SEM), and photoluminescence (PL) spectra were utilized to characterize thephosphors. The optimal concentration of Ce3+ ions in Ca19Zn2(PO4)14:Ce3+ phosphors is found to be x = 0.05. The energy transfer process from Ce3+ to Tb3+ is determined to the dipole–dipole interaction mechanism. The emissive colors of Ca19Zn2(PO4)14:Ce3+,Tb3+,Mn2+ phosphors can be effectively realized by energy transfer strategy. The bright white-light emission are successfully observed by adjusting the individual concentrations of Ce3+, Tb3+ and Mn2+ ions in Ca19Zn2(PO4)14 phosphors excited by UV light. The obtained results suggest the presented Ca19Zn2(PO4)14:Ce3+,Tb3+,Mn2+ phosphors can be potentially a candidate for single-phase white-light phosphor for UV-pumped sources.