A kind of well-ordered multilayer structure of octadecylamine-coated nanogolds with the mean diameter of 6.8nm was created layer by layer by the Langmuir–Blodgett method. Transmission electron microscopy (TEM) images and small-angle X-ray diffraction (SAXRD), respectively confirmed that the particles were well-ordered on each monolayer and aligned in layer by layer. UV–vis absorption spectra characterized optical properties of the well-ordered multilayer structure.