A series of BaLi 2 Al 2 Si 2 N 6 (BLASN): xEu 2+ phosphors are successfully synthesized and their crystal structure and luminescence properties under varying hydrostatic pressures are reported herein. Structure variation is analyzed using in situ high-pressure X-ray diffraction and Rietveld refinements. Based on decay curves and Gaussian fitting of emission spectra, the presence of two photoluminescence centers is demonstrated. BaLi 2 Al 2 Si 2 N 6 : 0.01Eu 2+ exhibits an evident peak position shift from 532 to 567 nm with an increase in pressure to ≈20 GPa. The possible factors and mechanisms for the variations are studied in detail. At a pressure of 16 GPa, BLASN: Eu 2+ realizes a narrow yellow emission with a full width at half maximum of ≈70 nm. The addition of BLASN: Eu 2+ (16 GPa) to the commercial white light-emitting diodes combination consisting of an InGaN chip, β-SiAlON: Eu 2+ , and red K 2 SiF 6 :Mn 4+ , can increase the color gamut by ≈15%, demonstrating the promising potential of pressure-driven BLASN: Eu 2+ for wide-color gamut spectroscopy applications. Moreover, the emission shifts arising from pressure variation and the distinct color changes enable its potential utility as an optical pressure sensor; the material exhibits high pressure sensitivity (dλ/dP ≈ 1.58 nm GPa −1 ) with the advantage of visualization.