Optical thermometry based on Y3Al5O12 (YAG) single crystal optical fiber with end Tm3+/Yb3+ co-doped is presented. The YAG crystal fiber with end Tm3+/Yb3+ co-doped was grown by laser heated pedestal growth (LHPG) method. Under a 976 nm laser diode excitation, the upconversion (UC) emissions, originating from 3F2,3→3H6 and 3H4→3H6 transitions of Tm3+ ions, were investigated in the temperature range from 333 K to 733 K. Interestingly, the UC emission intensity of 3F2,3→3H6 transition was significantly enhanced with increase of temperature, as compared with the other Tm3+/Yb3+ co-doped materials. The temperature dependence of fluorescence intensity ratio (FIR) of these two emission bands (3F2,3/3H4→3H6) suggests that this doped YAG crystal fiber can be used as a highly sensitive optical thermal probe, which demonstrates a high absolute sensitivity with the maximum value of 0.021 K−1 at 733 K. In addition, due to the compact structure, strong mechanical strength and high thermal stability, such thermal probe may be a more promising candidate for temperature sensor with a high spatial resolution.