M5(PO4)3 F:Eu2+ (M = Ca and Ba) co‐doped with Ce3+ phosphors were successfully prepared by the combustion synthesis method. The introduction of co‐dopant (Ce3+) into the host enhanced the luminescent intensity of the M5(PO4)3 F:Eu2+ (M = Ca and Ba) efficiently. Previously, we have reported the synthesis and photoluminescence properties of same phosphors. The aim of this article is to report energy transfer mechanism between Ce3+➔Eu2+ ions in M5(PO4)3 F:Eu2+ (M = Ca and Ba) phosphors, where Ce3+ ions act as sensitizers and Eu2+ ions act as activators. The M5(PO4)3 F:Eu2+ (M = Ca and Ba) co‐doped with Ce3+ phosphor exhibits great potential for use in white ultraviolet (UV) light‐emitting diode applications to serve as a single‐phased phosphor that can be pumped with near‐UV or UV light‐emitting diodes. Copyright © 2013 John Wiley & Sons, Ltd.