Recent advances in the characterization of the glassy aluminosilicate phases in coal fly ashes are reviewed and discussed in terms of the development of new models describing their mechanism of formation, composition, structural relationships and chemical reactivity. Characterization techniques such as electron microscopy, x-ray diffraction, infrared and Raman spectroscopy, nuclear magnetic resonance and Mössbauer spectroscopies, thermal analysis, acid dissolution, silanation, and density fractionation have been used as experimental probes, and reveal a range of information relating to the glass phases from the macro, through the micro, to the nano-structural levels. Complex inter- and intra-particle heterogeneity in ash is observable not only in bulk chemical and mineralogical analyses but also at the molecular level in the constituent glasses. Remarkable relationships between ash particle size, density and glass composition have been observed and lead to a new proposed mechanism for ash morphogenesis based on temperature-viscosity effects in the mineral precursor melts in the boiler flame. A glass-ceramic model for fly ash particle structure is proposed and discussed in terms of phase relations in the CaO–SiO2–Al2O3 and FeO–Fe2O3–A12O3–SiO2 systems, modification of the aluminosilicate glasses by alkali and alkaline earth metal cations, and microheterogeneity involving glass devitrification and phase separation.