Adsorption behavior of binary mixed alkanethiol molecules of octanethiol (OT) and dodecanethiol (DDT) on An substrate has been investigated with a variation of molar fraction in solution at room temperature. Linear-scan voltammograms (LSV) taken from the binary mixed self-assembled monolayer (SAM) on Au/Si showed a single reductive desorption peak, continuously shifting with a variation of mixing ratio in solution. Molecule-resolved scanning tunneling microscope (STM) images obtained from the binary SAM on Au/mica showed the phase separation with a few nanometer sized domains. The difference in the chain length between OT and DDT was not large enough to induce the phase separation with much larger domains, which could be well detected by LSV. There was no preferential adsorption of DDT to OT. (c) 2005 Elsevier B.V. All rights reserved.