Single-phase white-emission phosphors possess a judicious usage potential in phosphor-converted white-light-emitting diodes (WLEDs). Recently, numerous efforts have been made toward the development of new patterns of white-emitting phosphors that achieve excellent quantum yield, superior thermal stability, and applaudable cost effectiveness of WLEDs. Finding suitable single-component white phosphor hosts to provide an ideal local environment for activators remains urgent. Inspired by the original discovery of the promising host MgIn2(P2O7)(2) (MIP) and its structural dependence on alkali-metal cations, we synthesized a brand-new phosphor host, SrIn2(P2O7)(2) (SIP), via the traditional solid-state reaction. Its crystal structure was determined using an ab initio analysis and the Rietveld method. It belongs to a monoclinic unit cell with the space group C2/c. Besides, SIP exhibits a special layered three-dimensional framework in which the monolayer [SrO10](infinity) was surrounded by a bilayer [In2P4O14](infinity) made of the InO6 octahedra and P2O7 groups. A series of pure SIP:Tm3+,Dy3+ phosphors with tunable blue-white-yellow emission were prepared by adjusting the dopant concentration and utilizing the Tm3+-Dy3+ energy transfer. The daylight-white-emitting phosphor SIP:0.01Tm(3+),0.04Dy(3+) (the correlated color temperature is 4448 K) exhibits an abnormal thermal antiquenching property, and the emission intensity of 423 K reaches 103.7% of the initial value at 300 K. On the basis of the temperature-dependent lattice evolution and microenvironment analysis, the reduction of beta and lattice distortion can lead to lower asymmetry of the activators and benefit the compensation of trapped-electron thermal activation. In this work, an integration study was carried out on the crystal structure of the new matrix, the occupation of the luminescent center, the interaction of different activators in the host, and the distortion degree of the local structure for the activators, which is of great practical sense for producing a novel single-matrix white phosphor possessing superior thermal endurance for UV-light-stimulated WLEDs.