Samples of natural sodalite, Na8Al6Si6O24Cl2, submitted to gamma irradiation and to thermal treatments, have been investigated using the thermoluminescence (TL) and electron paramagnetic resonance (EPR) techniques. Both, natural and heat-treated samples at 500°C in air for 30 min, present an EPR signal around g = 2.01132 attributed to oxygen hole centers. The EPR spectra of irradiated samples show an intense line at g = 2.0008 superimposed by a hyperfine multiplet of 11 lines due to an O- ion in an intermediate position with respect to two adjacent Al nuclei. In the TL measurements, the samples were annealed at 500°C for 30 min and then irradiated with γ doses varying from 0.001 to 20 kGy. All the samples have shown TL peaks at 110, 230, 270, 365, and 445°C. A correlation between the EPR g = 2. 01132 line and the 365°C TL peak was observed. A TL model is proposed in which a Na+ ion acts as a charge compensator when an Al3+ ion replaces a Si4+ lattice ion. The γ ray destruction of the Al-Na complex provides an electron trapped at the Na and a hole trapped at a non-bridging oxygen ion adjacent to the Al3+ ion. © Springer-Verlag 2009.