Multi‐mode optical thermometry is emerging as a promising technique for accurate temperature measurement. Here, a series of Na2GdMg2V3O12:Sm3+ (NGMVO:xSm3+) phosphors with dual‐emission centers were successfully elaborated. Irradiated by 349 nm light, NGMVO:Sm3+ can generate emissions from VO43− and Sm3+ simultaneously due to energy transfer between them. Benefitting from difference of thermal quenching performance of two luminescent centers, fluorescence intensity (FI), fluorescence intensity ratio (FIR), and Commission Internationale de L'Eclairage coordinate modes of NGMVO:Sm3+ thermometer were designed. Maximum relative sensitivities (SR) are found to be as high as 2.21 %K−1, 2.12 %K−1, and 0.244 %K−1, respectively. Besides, with temperature increasing, SR values of FI and FIR modes decrease slowly. Their minimal SR values between 303 and 513 K maintain above 1.36 %K−1 and 1.08 %K−1, respectively. Our findings reveal that NGMVO:Sm3+ phosphors have promising applications for multimode temperature senor.