Self-assembled monolayers (SAMs) of 1,5-pentanedithiol and 1,9-nonanedithiol on Au (111) surfaces were used to adsorb copper ions (Cu2C) from an ethanolic solution of cupric chloride (CuCl2) by chemical interaction of thiol groups and copper ions assembling multilayer structures. Ellipsometry, contact angle measurement and X-ray photoelectron spectroscopy (XPS) confirmed that the alkanedithiol molecules formed SAMs with only one-ended thiol groups attached to the gold surface, leaving the other-ended thiol groups free, which is supported by the molecular mechanics calculation. XPS and X-ray Auger electron spectroscopy (XAES) not only indicate that copper ions deposited onto SAMs from the solution by the chemical reaction of copper ions with ended free thiol groups of SAMs, but more importantly demonstrate that copper is present in the C1 oxidation state in the multilayer system. Atomic force microscopy (AFM) was used to observe SAMs and multilayer structures.