In the development of materials resistant to thermal shock, materials with negative or near zero thermal expansion have been of vital importance in recent years. The A2M3O12 family of ceramics (A = trivalent cation, M = hexavalent cation) has promising characteristics to avoid thermal shock rupture, due to its atypical thermal expansion properties. Within this family is the Al2W3O12 ceramic, which has unique thermal properties and this allows its use in conditions of thermal shock. However, changes in the crystal lattice caused by point defects can generate alterations in this material. Al2W3O12 ceramic can contain defects such as oxygen vacancies, which affect optical, thermal and other properties. The goal of this study is to study the influence of oxygen vacancies on the properties of Al2W3O12 ceramics, as well as the importance of temperature and atmosphere in the generation of oxygen vacancies. The Al2W3O12 phase was exposed to two atmospheres (H2 and Ar) at controlled temperatures: 300 degrees C, 400 degrees C and 500 degrees C to generate oxygen vacancies. The ceramic obtained was characterized by X-ray power diffraction (XRPD), diffusion reflectance spectroscopy (DRS), electron paramagnetic resonance spectroscopy (EPR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermal conductivity test. The influence of oxygen vacancies on the coefficient of thermal expansion and thermal conductivity in calcined samples in non-oxidizing atmospheres was demonstrated. Samples calcined at 500 degrees C revealed high absorption of the ultraviolet and visible spectra compared to the samples calcined 300 degrees C and 400 degrees C. In addition, different states of reduced valence of W were found (such as W5+ and W4+), through the XPS technique, in order to compensate of oxygen vacancies, that were confirmed by EPR and Raman analysis.