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The mechanism of gold solvent extraction from KAu(CN)2 solution was investigated by means of FTIR, EXAFS, ICP and radioactive tracer methods. Two extraction systems were studied, namely N263-tributyl phosphate(TBP)-n-dodecane and N263-iso-octanol-n-dodecane. High-reso- lution FT IR spectroscopy indicated that the CN stretching vibrations of the two extraction systems differred greatly. In order to interpret the significant difference in CN stretching vibrations, two extracting species models are proposed supramolecular structures based on the formation of hydrogen bonds between Au(CN)2- and modifiers such as TBP and iso-octanol.