Lanthanide-doped luminescent materials have drawn great attention due to their lighting, display, and sensing applications. However, their emission intensity usually decreases with increasing temperature, leading to a weaken performance. In this work, the Er3+-doped Yb2Mo3O12 microcrystals with optical temperature sensing properties have been synthesized by a solid-phase sintering route. Under the excitation of a 980 nm laser, the sample shows enhanced upconversion emissions as temperature rises, which is attributed to the negative thermal expansion in the crystal structure and enhanced crystal field strength. At the same time, based on the luminous intensity ratio of two thermally coupled energy levels (Er3+:2H11/2,4S3/2), the temperature sensing properties of the prepared microcrystals were studied. This work achieves high SR (1207.4/T) in the range from 313 to 573 K, and it is accompanied by a 21-fold enhancement of the upconversion emission intensity. As a whole, this is an excellent material that can be used for optical temperature sensing with highly sensitive and enhanced upconversion emission.