Li2SiO3:Sm was synthesized by the solution combustion method. Powder x-ray diffraction technique was used to find the phase formation. Li2SiO3:Sm exhibits thermoluminescence (TL) peaks at approximately 140°C, 155°C, 190°C, 250°C, and 405°C. Three defect centers contribute to the observed electron spin resonance spectrum from the gamma irradiated phosphor. Center I with principal g-values g|| = 2.0206 and g⊥ = 2.0028 is identified as an O2− ion while center II, with an isotropic g-factor 2.0039, is assigned to an F+-type center. Center III is assigned to a Ti3+ center. The Ti3+ center is related to the 250°C TL peak while the O2− ion also correlates with the main TL peak at 250°C. An additional defect center is observed during thermal annealing experiments, and the center (assigned to F+ center) seems to originate from an F center. The F center appears to be associated with the high temperature TL peak in a Li2SiO3:Sm phosphor. The luminescence spectrum reveals the dominant emission peaks at 605 (4G5/2 → 6H7/2) nm under the excitation wavelength of 402 nm.