How to improve the sensitivity of the temperature‐sensing luminescent materials is one of the most important objects currently. In this work, to obtain high sensitivity and learn the corresponding mechanism, the rare earth (RE) ions doped Y4.67Si3O13 (YS) phosphors were developed by solid‐state reaction. The phase purity, structure, morphology and luminescence characteristics were evaluated by XRD, TEM, emission spectra, etc. The change of the optical bandgaps between the host and RE‐doped phosphors was found, agreeing with the calculation results based on density‐functional theory. The temperature‐dependence of the upconversion (UC) luminescence revealed that a linear relationship exists between the fluorescence intensity ratio of Ho3+ and temperature. The theoretical resolution was evaluated. High absolute (0.083 K−1) and relative (3.53% K−1 at 293 K) sensitivities have been gained in the YS:1%Ho3+, 10%Yb3+. The effect of the Yb3+ doping concentration and pump power on the sensitivities was discussed. The pump‐power–dependence of the UC luminescence indicated the main mechanism for high sensitivities in the YS:1%Ho3+, 10%Yb3+. Moreover, the decay‐lifetime based temperature sensing was also evaluated. The above results imply that the present phosphors could be promising candidates for temperature sensors, and the proposed strategies are instructive in exploring other new temperature sensing luminescent materials.