An in-depth study of Al2W3O12 negative thermal expansion (NTE) ceramic was performed, focused on synthesis, phase mappings, and the underlying mechanisms shown to be responsible for NTE. Review of the literature has shown inconsistencies in reported values of the dilatometry measured coefficients of thermal expansion, and the temperature for the known monoclinic to orthorhombic phase transition. Two synthesis techniques are introduced: an ionic-liquid non-hydrolytic sol-gel synthesis route; and a low temperature solid state reaction synthesis for Al2W3O12. X-ray diffraction, Raman spectroscopy, and attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR) were used to verify the techniques. Two differential scanning calorimetry (DSC) experiments (high and low temperature) were performed on the material showing the transition between -5 and -20 °C and no other phase changes until a reported degradation above 1100 °C. Extensive dilatometry on the material led to the discovery of elastic transitions occurring in the polycrystalline sample capable of explaining the inconsistencies in reported dilatometry results. This is further developed into a proposed model defining the regions between these transitions. Each region has a different thermal expansion as well as a direct effect on the reaction of the material upon cooling. This proposed model may allow more consistent reporting of dilatometry results for NTE materials. Raman spectroscopy was performed from 25-725 °C on the material showing both a joining in the tungsten-oxygen bending modes as well as a broadening in the tungsten-oxygen stretching modes. This is consistent with Al-O-W angle changes along the same temperature range reported in literature as well as the transverse vibrational modes responsible for NTE.