We describe a synthesis of Au wavy nanowires in an aqueous solution in the presence of cetyltrimethylammonium bromide (CTAB). The resultant Au nanowires automatically separated from the solution and floated at the air/water interface. We investigated the formation mechanism by characterizing the samples obtained at different stages of the synthesis. Both particle attachment and cold welding were found to be involved in the formation of such nanowires. Based on X-ray photoelectron spectroscopy and thermogravimetric analysis, the CTAB molecules adsorbed on the surface of a Au nanostructure went through a change in structure from a bilayer to a monolayer, converting the Au surface from hydrophilic to hydrophobic. As a result, the Au wavy nanowires were driven to the air/water interface during the synthesis. This growth mechanism is potentially extendable to many other systems involving small surfactant molecules.