A fluoride material phosphor doped with rare earth ions Eu3+ and Dy3+ was studied for its photoluminescence (PL) properties. The material was synthesized using a combustion method and characterized using X‐ray diffraction (XRD) and PL techniques. The Na3Ca2(SO4)3F: Eu3+ phosphor exhibits two distinct peaks at 593 nm (orange) and 615 nm (red) at an excitation wavelength of 395 nm. The PL excitation spectrum of the Na3Ca2(SO4)3F: Dy3+ phosphor showed series of peaks, corresponding to the 4f → 4f transitions of Dy3+ ions. Under 350‐nm excitation, the PL emission spectrum revealed two prominent bands one at 483 nm (blue region) due to the 4F₉/₂ → 6H₁₅/₂ transition, and another at 573 nm (yellow region) resulting from the 4F₉/₂ → 6H₁₃/₂ transition. These blue and yellow emissions suggest potential applications in solid‐state lighting, particularly for mercury‐free excitation sources. Rare earth–doped Eu3+/Dy3+ materials exhibit highly efficient PL properties, making them suitable candidates for white light‐emitting diodes (LEDs) or other solid‐state lighting phosphors.