In this work, novel green-emitting La₂MgTiO₆:Er³⁺ (LMTO:Er³⁺) phosphors were successfully synthesized. The phase structure, electronic structure, morphology, luminescence behaviors, and other optical characteristics were investigated in detail. Besides, the optical sensing properties of the thermal-coupled levels (²H₁₁/₂, ⁴S₃/₂) were investigated based on the fluorescence intensity ratio principle, and the maximum absolute and relative sensing sensitivities were found to be as high as 0.963% and 1.107% K–¹, respectively. The packaged light-emitting diode (LED) emitted the near-white light with a color-rendering index of 77.12 and a proper correlated color temperature of 4989 K, respectively. Finally, the novel polydimethylsiloxane film-converted LED structure was fabricated. All the above results suggest that the novel LMTO:Er³⁺ phosphors are proposed for solid-state lighting and luminescent thermometers.