<p>A series of novel blue-emitting Sr₃CeNa(PO₄)₃F:Eu²⁺ (SCNPOF:Eu²⁺) phosphors were synthesized through solid-state reaction. The as-prepared phosphor shows a blue light emission ranging from 350 ~ 550&#xa0;nm centered at 447&#xa0;nm under 340&#xa0;nm UV light excitation, attributed to the 4f-5d transition of Eu²⁺. The energy transfer mechanism from Ce³⁺ to Eu²⁺ was identified as dipole–dipole interaction, and the energy transfer efficiency and critical distance were calculated. Subsequently, a white light-emitting diode (WLED) with a color rendering index of 94 was fabricated by combining a 365&#xa0;nm UV-LED chip with the as-prepared blue-emitting SCNPOF:Eu²⁺ phosphor, commercial green (Ba, Sr)₂SiO₄:Eu²⁺ phosphor, and red CaAlSiN₃:Eu²⁺ phosphor. The results indicate that the SCNPOF:Eu²⁺ phosphors have potential application in UV-based WLEDs.</p>