The development of an efficient blue phosphor with remarkable thermal stability required for high-quality white-light-emitting diodes (WLEDs) remains an exigent task and mainly concerned BaMgAl10O17:Eu2+ (BAM:Eu). Despite the outstanding performance of BAM:Eu, the reduction in luminescence efficiency under long-term operation results in numerous researches on new hosts having lattice rigidity with symmetrical coordination environment. Therefore, we have synthesized a competent blue-emitting Eu2+-activated Sr5SiO4Cl6 (SSC) phosphors. The admirable rigidity of these phosphors with three Sr polyhedra Sr(I)O9, Sr(II)O7, and Sr(III)O8 assessed from Rietveld refinement indicate the dense connectivity in the crystal structure, and the ab initio calculations further support the firm electronic band structure. The broad excitation from 250 to 450 nm suitably matches the absorption band of a near-UV (n-UV) LED chip. The phosphor exhibited bright blue emission with internal quantum yield and color purity > 90% which contribute to the slender fwhm of 33 nm. The first-principle calculation indicates the most stable site for Eu2+ substitution as Sr(III)O8, and the experimental results agreed with this fact as well. The synthesized phosphor displayed an excellent thermal stability which is superior to that of the commercial BAM:Eu phosphor. The excellent thermal stability may be owed to the highly symmetric coordination environment of Eu2+ in the SSC host that are revealed from the distortion and charge density distribution calculation by density functional theory. The blue phosphor was further utilized for WLEDs and displayed white light with a high color-rendering index and suitable correlated color temperature, which is ideal for practical applications in warm WLEDs.