A novel orange-yellow-emitting Ba3Gd(PO4)3:x Eu2+,y Mn2+ phosphor is prepared by high-temperature solid-state reaction. The crystal structure of Ba3Gd(PO4)3:0.005 Eu2+,0.04 Mn2+ is determined by Rietveld refinement analysis on powder X-ray diffraction data, which shows that the cations are disordered on a single crystallographic site and the oxygen atoms are distributed over two partially occupied sites. The photoluminescence excitation spectra show that the developed phosphor has an efficient broad absorption band ranging from 230 to 420 nm, perfectly matching the characteristic emission of UV-light emitting diode (LED) chips. The emission spectra show that the obtained phosphors possess tunable color emissions from yellowish-green through yellow and ultimately to reddish-orange by simply adjusting the Mn2+ content (y) in Ba3Gd(PO4)3:0.005 Eu2+,y Mn2+ host. The tunable color emissions origin from the change in intensity between the 4f–5d transitions in the Eu2+ ions and the 4T1-6A1 transitions of the Mn2+ ions through the energy transfer from the Eu2+ to the Mn2+ ions. In addition, the mechanism of the energy transfer between the Eu2+ and Mn2+ ions are also studied in terms of the Inokuti–Hirayama theoretical model. The present results indicate that this novel orange-yellow-emitting phosphor can be used as a potential candidate for the application in white LEDs.