Eu3+-activated La2LiSbO6 were prepared via solid-state reaction and characterized by Rietveld refinements. The phosphor crystallizes in the monoclinic perovskite of space group P21/n with framework constructed by the ordering of (Li,Sb)O6 octahedra. The photoluminescence (PL) spectra, decay lifetimes and absolute quantum efficiency (QE) were reported. The phosphor can be efficiently excited by near UV and blue light exhibiting bright red emission from the electric dipole transition 5D0→7F2 at 613nm. The maximum quantum efficiency can reach to 70%. The phosphor is a potential choice for lighting and display. The emission rise time of the 5D0 level of La2LiSbO6:Eu3+ was verified to be temperature dependent in a wide range from 7K to 300K. It could be exploited for temperature sensing for an application in luminescence thermometry.