An Eu2+-activated Sr8MgSc(PO4)7:Eu2+ yellow-emitting phosphor with strong luminescence was synthesized and its crystal structure has been refined and determined from the XRD profiles using synchrotron light source by Rietveld refinement method. Non-radiative transitions between Eu2+ ions in the Sr8MgSc(PO4)7 host have also been demonstrated to be attributable to dipole–dipole interactions, and the critical distance was estimated to be 24.83 A by using spectral overlap methods. In addition, white-light near-UV LEDs were fabricated by using a phosphor blend of composition-optimized yellow-emitting Sr8MgSc(PO4)7:0.01Eu2+ and blue-emitting BaMgAl10O17:Eu2+ commodity pumped with a 400 nm near-UV chip and the Ra value and reduced color temperature of were found to be 96.7 and 5,614 K, respectively. These results indicate that yellow-emitting Sr8MgSc(PO4)7:xEu2+ can serve as a promising candidate for application in white-light LEDs.