A comprehensive approach to qualitative and quantitative characterization of crystalline and amorphous constituent phases of a largely heterogeneous Class F fly ash is presented. Traditionally, fly ash composition is expressed as bulk elemental oxide content, generally determined by X-ray fluorescence spectroscopy. However, such analysis does not discern between relatively inert crystalline phases and highly reactive amorphous phases of similar elemental composition. X-ray diffraction was used to identify the crystalline phases present in the fly ash, and the Rietveld quantitative phase analysis method was applied to determine the relative proportion of each of these phases. A synergistic method of X-ray powder diffraction, scanning electron microscopy, energy dispersive spectroscopy, and multispectral image analysis was developed to identify and quantify the amorphous phases present in the fly ash.