Sm 3+ , Mn 4+ co-activated LaGaO 3 phosphors, giving the characteristic emissions of orange and red emission simultaneously, were prepared by a solid-state reaction. Their luminescence properties, energy transfer behavior, thermal stability, and ratiometric temperature sensing performance were investigated. Thanks to the inhibition of energy transfer between Sm 3+ and Mn 4+ ions at high temperature and the reconstruction of the traps, the distinct optical behavior of the involved activators dependent on the ambient temperature was evaluated. Antithermal quenching performance of Sm 3+ ions along with the emission declination of Mn 4+ ions was observed. Hence, the optical thermometry characteristics of the resultant phosphor based on the fluorescent intensity ratio (orange/red) realize a recorded temperature sensitivity of 4.19% K −1 and 2.09% K −1 . Moreover, the as-explored film combined with the LaGaO 3 : Sm 3+ , Mn 4+ phosphor is demonstrated to be a promising multi-color optical thermometer.