A series of single-phase broadband white-light-emitting Sr₅(PO₄)₃F:Eu²⁺,Mn²⁺ phosphors were prepared by a solid state reaction. The luminescence property, and the crystal and electronic structures of the fluorophosphates were studied by photoluminescence analysis, XRD Rietveld refinement and density functional theory calculation (DFT), respectively. Under near ultraviolet excitation in the 250 to 430 nm wavelength range, the phosphors exhibit two emission bands centered at 440 and 556 nm, caused by the Eu²⁺ and Mn²⁺ ions. By altering the relative ratios of Eu²⁺ and Mn²⁺ in the compounds, the emission color could be modulated from blue to white. The efficient energy transfer from the Eu²⁺ to Mn²⁺ ions could be ascribed to the well crystallized host lattice and the facile substitution of Eu²⁺ and Mn²⁺ for Sr²⁺ sites due to similar ionic radii. A series of fluxes were investigated to improve the photoluminescence intensity. When KCl was used as flux in the synthesis, the photoluminescence intensity of Sr₅(PO₄)₃F:Eu²⁺,Mn²⁺ was enhanced by 85% compared with no fluxes added. These results demonstrate that the single-phase Sr₅(PO₄)₃F:Eu²⁺,Mn²⁺ with enhanced luminescence efficiency could be promising as a near UV-convertible direct white-light-emitting phosphor for WLED applications.