Incineration is in many countries a common treatment method for municipal solid waste, and utilization of the ash residues has attracted significant interest. The bottom ash is best suited as a secondary construction material, whereas the fly ash is being investigated as a secondary raw material for recovery of, for example, Zn, Cu, and salts. For both types of application, knowledge about the chemical speciation of Zn and Cu in the ashes is valuable. The present work focuses on identifying and quantifying the chemical species of Zn and Cu in 12 samples of fly ash and bottom ash from three waste-to-energy plants using X-ray absorption near edge structure (XANES). The XANES spectra of the ash samples showed similar distinctive features, and both in the bottom and fly ash samples, the same chemical forms were identified but in various ratios. Cu and Zn occurred in several chemical forms, with typically 5-7 forms present in the same sample. For Cu, the XANES spectra of the fly ash samples were nearly identical, indicating very similar chemical speciation (same chemical forms and similar ratios). Cu was found to exist in various oxide, hydroxide, chloride, silicate, and metallic forms. The most commonly occurring Zn compounds were the aluminate, ferrite, silicate, and oxide along with chloride, basic carbonate (hydrozincite), and occasionally metallic forms, probably alloyed with Cu in brass. Cu occurred in different oxidation states from zero to +II, with a higher prevalence of the lower oxidation states in bottom ash than in fly ash. Zn occurred mainly in oxidation state +II in all ashes analyzed. Finally, we showed that during outdoor storage of bottom ash, levels of Cu and Zn hydroxycarbonates were increased compared to fresh bottom ash. This carbonate formation aims to make Cu and Zn less leachable.