Although some researchers have reported that chlorides may play an important part in the evaporation of copper during heat treatment of municipal solid waste incinerators (MSWI) fly ash (1, 2) , details on the copper speciation in volatile matters (secondary fly ash, SFA) are still lacking. In this work, we used in situ X-ray absorption spectroscopy (XAS) experiments involving three types of SFA, which was collected from a high-temperature tubular electric furnace by thermal treatment of municipal solid waste incinerator (MSWI) fly ash at 1000, 1150, and 1250 degrees C. The results obtained by a linear combination fit (LCF) of X-ray absorption near edge structure (XANES) spectra revealed that in MSWI fly ash copper mainly exists as CuO and CuSO(4).5H(2)O while chloride almost dominated all the content of the SFA conformation, which was more than 80%. Extended X-ray absorption fine structure (EXAFS) data analysis indicated the presence of both Cu-O and Cu-Cl bonds in the first coordination shell of Cu ions in all SFA, while only Cu-O bonds occur in the MSWI fly ash. Consequently, in the MSWI fly ash during heat treatment copper evaporated as chloride, and the latter plays an important role in the formation of copper chloride.