Non‐contact temperature sensors based on the fluorescence intensity ratio (FIR) have been widely investigated owing to their high sensitivity and reliable real‐time monitoring. Herein, the SiO2‐coated LiY(MoO4)2@SiO2:Er3+,Yb3+ phosphor was investigated as an optical thermometry material, which was synthesized using the conventional solid state reaction and coated by a facile wet chemical route. The effect of surface modification on FIR was systematically characterized by structural analyses and spectral measurements and the temperature‐dependent up‐conversion FIR was investigated from 303 to 603 K under a 980 nm laser excitation. The results showed that the FIR value was thermally stable and the SiO2 coating led to a higher FIR sensitivity as well as a higher saturation threshold. This work would pave a way to design interesting optical thermometry materials in up‐conversion phosphors with better properties.