A series of Sm³⁺ activated Lu₂MoO₆ phosphors were synthesized by high-temperature solid-state reaction method. The X-ray diffraction (XRD) patterns, excitation spectra, emission spectra and decay lifetime of the phosphors were measured to characterize the structural and luminescent properties. The crystal structure of Lu₂MoO₆:Sm³⁺ has been defined by the Rietveld method, and it is shown that Lu₂MoO₆:Sm³⁺ belongs to the monoclinic system. The photoluminescence (PL) excitation spectra revealed that the obtained phosphors can be efficiently excited by both near-ultraviolet and blue light. Under 360 and 402 nm excitation, four dominating emission bands corresponding to the ⁴G_5/2→ ⁶H_J (J = 11/2, 9/2, 7/2, and 5/2) transitions of Sm³⁺ ions were detected. The emission intensity was strongly dependent on Sm³⁺ concentration and the optimal doping concentration in the Lu₂MoO₆:Sm³⁺ phosphor was determined to be 5 mol%. The concentration quenching mechanism was investigated using the Van Uitert equation and Inokuti-Hirayama (I-H) model. In addition, the thermal quenching mechanism of Sm³⁺ activated Lu₂MoO₆ has been proposed. The Lu₂MoO₆:Sm³⁺ phosphors have potential application in temperature sensors based on luminescent intensity and lifetime.