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Recently, lanthanide-ion-doped luminescent materials have been extensively used as optical thermometry probes due to their fast responses, non-contact, and high sensitivity properties. Based on different responses of two emissions to temperature, the fluorescence intensity ratio (FIR) technique can be used to estimate the sensitivities for assessing the optical thermometry performances. In this study, we introduce different doping concentrations of Eu3+ ions into negative thermal expansion material Sc2W3O12 to increase the thermal-enhanced luminescence from 373 K to 548 K, and investigate the temperature sensing properties in detail. All samples can exhibit their good luminescence behaviors thermally enhanced. The emission intensity of Sc2W3O12:6-mol% Eu3+ phosphor reaches 147.8% of initial intensity at 473 K. As the Eu3+ doping concentration increases, the resistance of the sample to thermal quenching decreases. The FIR technique based on each of the transitions 5D→ 7F1 (592 nm) and 5D→ 7F2 (613 nm) of Eu3+ ions demonstrates a maximum relative temperature sensitivity of 3.063% K−1 at 298 K for Sc2W3O12:6-mol% Eu3+ phosphor. The sensitivity of sample decreases with the increase of Eu3+ concentration. Benefiting from the thermal-enhanced luminescence performance and good temperature sensing properties, the Sc2W3O12:Eu3+ phosphors can be used as optical thermometers. [ABSTRACT FROM AUTHOR]