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In this work, we studied the reaction between Au nanoparticles (Au NPs) and [Fe(CN)(6)](3-) by the UV-vis absorption spectroscopy, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy. The absorption peak of Au NPs disappeared after adding [Fe(CN)(6)](3-) and the XPS data conformed the formation of [Au(CN)(2)](-). The results demonstrated that [Fe(CN)(6)](3-) could induce the dissolution of Au NPs, where the CN- from the dissociation of [Fe(CN)(6)](3-) played an important role.