Containerless liquid-phase processing methods were used to synthesize two glasses, both containing alumina (A), yttria (Y), and lanthana (L), and one containing similar to 20 mole% silica (S) as well. In both materials, denoted AYL and AYLS, alumina is the dominant component (> 50 mole%), and the lanthana:yttria ratio is similar to 2:1. A variety of experimental techniques, e.g. X-ray diffraction, high-field Al-27 magic angle spinning-nuclear magnetic resonance (MAS-NMR), differential scanning calorimetry, and neutron diffraction, were used to analyze both the structure of the amorphous phases resulting from liquid-phase processing and subsequent thermal treatments, and the thermodynamic properties of the as-made and heat-treated materials. The results of the experiments on these glasses and liquids have elucidated the nature of the transitions occurring between the glass transition and crystalline regimes, and have enabled the synthesis of a novel class of alumina-based nanomaterials.