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The optical temperature sensor utilizing the fluorescence intensity ratio (FIR) has garnered significant attention in the past few years due to its rapid response, robust anti-interference capability, remote control feature, and other advantages. In this study, the high-temperature solid-phase approach was used to fabricate a variety of double perovskite-structured La₂MgSnO₆: Bi³⁺, Sm³⁺ (LMS: Bi³⁺, Sm³⁺) phosphors. The Rietveld refinement data of XRD and the Gaussian fitting of the emission peak of LMS: 0.02Bi³⁺ phosphor indicated Bi³⁺ occupies three lattice sites. The calculation and analysis of average lifetime and energy transfer efficiency substantiated the presence of energy transfer from Bi³⁺ to Sm³⁺, with a transfer efficiency of up to 59.07%. The emission intensity of LMS: 0.02Bi³⁺, 0.05Sm³⁺ at 403 K maintains 50.2% at the condition of room temperature. The FIR fitting and calculation demonstrated that LMS: 0.02Bi³⁺, 0.05Sm³⁺ phosphor possessed good optical temperature sensitivity, with a maximum absolute sensitivity S_a-max of 0.0055 K⁻¹ and a maximum relative sensitivity S_r-max of 0.88% K⁻¹, demonstrating its valuable potential applications for optical temperature sensors.