In recent years, with the increasing demand for non-contact temperature measurement, it is urgent to develop a new type of phosphor with double emission centers, high sensitivity and good reliability. A series of Bi3+and Eu3+ co-doped La2LiSbO6 double emission center phosphors were successfully prepared. The response characteristics of Bi3+and Eu3+ at different temperatures in the range of 293–473k were calculated by fluorescence intensity ratio (FIR) technique. The optimal relative sensitivity Sr and absolute sensitivity Sa were 1.13 % K−1 and 1.27 % K−1, respectively. Hence, La2LiSbO6:Bi3+, Eu3+ phosphors have the capability of non-contact optical temperature measurement and are a promising material for application. The phosphor is combined with the optical fiber temperature sensor to monitor the real-time temperature of the computer central processing unit. The optical fiber temperature sensor system breaks through the limitations of traditional temperature measurement, and can be used in special environments such as small size and strong electromagnetic interference. It has become an ideal choice to replace the traditional temperature sensor.