The crystal structure of Ca4Si2O7F 2:Eu2+,Mn2+ was refined and determined from X-ray diffraction (XRD) profiles obtained using a synchrotron light source by the Rietveld refinement method. It was found to crystallize into a monoclinic structure with the P21/c(14) space group. On examining the Mn 2+-concentration-dependent photoluminescence properties, we found that the emission colors could be tuned from blue (0.152, 0.112) to white-light (0.351, 0.332) and eventually to yellow (0.430, 0.423) through energy transfer by changing the Eu2+/Mn2+ ratio. Moreover, energy transfer from a sensitizer Eu2+ to an activator Mn2+ occurs via a resonance-type dipole-quadrupole interaction mechanism, and the critical distances of the energy transfer were calculated to be 11.66 Å and 12.61 Å using concentration quenching and spectral overlap methods, respectively. Combining a 400 nm near-ultraviolet (NUV) chip and a single-phase white-emitting (Ca0.96Eu0.01Mn0.03) 4Si2O7F2 phosphor produced a white-light NUV LED with CIE chromaticity coordinates of (0.347, 0.338) and a warm color temperature of 4880 K.