A series of novel temperature-sensitive phosphors LiAl5(1−x)O8: xCr3+ (x=0.001–0.012) are synthesized by combustion method. The phosphors can be efficiently excited by the whole wavelength range of the visible light, producing strong deepred emission, which can be assigned to the 2E→4A2 transition. The intensity, peak wavelength and decay lifetime of the emission are measured to vary strongly with temperature for all the samples. Especially, the decay lifetime change dramatically from 4.31ms to 0.38ms from 200K to 600K for the sample with x=0.002, which give a highest temperature sensitivity of −0.015msK−1 at 400K and a maximal relative sensitivity of 0.83% K−1 at 447K. These results show that LiAl5O8:Cr3+ is promising for optical thermometry.