Single-component white phosphors stand a good chance to serve in the next-generation high-power white light-emitting diodes. Because of low thermal stability and containing lanthanide ions with reduced valence state, most of reported phosphors usually suffer unstable color of lighting for practical packaging and comparably complex synthetic processes. In this work, we present a type of novel color-tunable blue-white-yellow-emitting MgIn2P4O14:Tm3+/Dy3+ phosphor with high thermal stability, which can be easily fabricated in air. Under UV excitation, the MgIn2P4O14:Tm0.02Dy0.03 white phosphor exhibits negligible thermal-quenching behavior, with a 99.5% intensity retention at 150 degrees C, relative to its initial value at room temperature. The phosphor host MgIn2P4O14 was synthesized and reported for the first time. MgIn2P4O14 crystallizes in the space group of C2/c (No. 15) with a novel layered structure built of alternate anionic and cationic layers. Its disordering structure, with Mg and In atoms co-occupying the same site, is believed to facilitate the energy transfer between rare-earth ions and benefit by sustaining the luminescence with increasing temperature. The measured absolute quantum yields of MgIn2P4O14:Dy-0.04, MgIn2P4O14:Tm0.01Dy0.04, and MgIn2P4O14:Tm0.02Dy0.03 phosphors under the excitation of 351 nm ultraviolet radiation are 70.50%, 53.24%, and 52.31%, respectively. Present work indicates that the novel layered MgIn2P4O14 is a promising candidate as a single-component white phosphor host with an excellent thermal stability for near-UV-excited white-light-emitting diodes (wLEDs).