The major oxide content and mineralogy of 75 European fly ashes were examined, and the major element composition of the glass phase was obtained for each. Correlation of compositional trends with the glass content of the ash was explored. Alkali content was deduced to have a major influence on glass formation, and this in turn could be related to the probable chemistry of clay minerals in the source coals. Maximal glass content corresponded to high aluminum content in the glass, and this is in accordance with the theoretical mechanism of formation of aluminosilicate glasses, in which network-modifying oxides are required to promote tetrahedral coordination of aluminum in glass chain structures. Iron oxide was found to substitute for alkali oxides where the latter were deficient, and some indications of preferred eutectic compositions were found. The work suggests that the proportion of the glass phase in the ash can be predicted from the coal mineralogy and that the utility of a given ash for processing into geopolymers or zeolites is determined by its source.