Coal ash released into the environment may release toxic trace elements into water, sediments, and soils. The objective of this study was to characterize the chemical speciation of As, Se, Cu, Zn, Cr, and U in coal fly ash samples related to the 2008 Kingston ash spill. Three ash samples were analyzed using X-ray absorption spectroscopy (XAS) to determine oxidation states or dominant species of trace elements, which were previously found to range in concentration from 8 to 20 mg kg(-1). Linear combination fitting (LCF) of X-ray absorption near edge structure (XANES) spectra from ash samples indicated that both reduced and oxidized forms of the trace elements were present in the fly ash samples. We used the mineralogical composition of the fly ash to select the most relevant standards for LCF fitting of XANES spectra, which included metal-doped glasses, trace elements sorbed to iron oxy(hydroxides), and pure mineral phases for each element. Arsenic K-edge XANES spectra were best fit as oxidized As(V) (95-100%) associated with iron phases or aluminosilicate glass, where selenium K-edge XANES spectra were fit as Se(W) (77-86%) associated with glass, with lesser proportions of Se(VI) and a more reduced Se species [fit as Se(0) or Se(II)S-2]. Zinc K-edge XANES spectra were best fit as Zn associated with ferrihydrite (70-77%), franklinite (ZnFe2O4, 8-12%), and ZnO (14-20%). Qualitative assessment of U L-m-edge and Cr K-edge XANES spectra showed dominances of U(VI) and Cr(III) oxidation states. Copper K-edge XANES data indicated the possibility of both reduced and oxidized species, although our analysis could not fully account for all spectral features. Our results revealed multiple species of each trace element in the fly ash samples, which is important for predicting environmental mobility and bioavailability under the range of geochemical conditions found in aquatic and terrestrial environments.