In recent years, phosphors have been used in the field of temperature sensing, which has aroused great interest because of its advantages of quick response, high sensitivity and high accuracy. However, exploring optical thermometers with ultra-high sensitivity remains a challenge. In this work, we have designed and synthesized Sm3+ and Mn4+ co-doped La3Mg2NbO9 phosphor for temperature sensing for the first time by utilizing the anomalous thermal quenching property of Sm3+ ions and the sensitive thermal quenching property of Mn4+ ions. Furthermore, the structure, elemental distribution, morphology and optical characteristics of La3Mg2NbO9:Sm3+,Mn4+ were studied in detail. Benefiting from the different responses of the Sm3+ and Mn4+ ions to temperature, the fluorescence intensity ratios of Sm3+ to Mn4+ in La3Mg2NbO9 samples show excellent optical thermometry performance in the range of 303 ∼ 463 K. The maximum absolute sensitivity (Sa) and relative sensitivity (Sr) values of La3Mg2NbO9:Sm3+,Mn4+ sample reach as high as 0.117 K-1 (@463 K) and 4.48 % K-1 (@303 K), respectively. Furthermore, the maximum of Sa is 0.385 K−1 (@463 K) and the maximum of Sr is 4.54 % K−1 (@303 K) based on the fluorescence lifetime temperature measurement method. The temperature cyclotron curve of the sample proves that the sample has excellent stability and repeatability in temperature measurement. These results demonstrate that the designed La3Mg2NbO9:Sm3+,Mn4+ phosphor is promising for the field of non-contact optical temperature thermometry.