Cysteinyl amino methylated β-cyclodextrin was adsorbed on Au(111) as well as on mercury electrode. Scanning probe microscopy and electrochemical techniques confirmed that a chemisorbed self-assembled monolayer (SAM) of the β-cyclodextrin is formed, proving that a single –SH moiety located in the cysteinyl group is sufficient to anchor the entire methylated β-cyclodextrin molecule to the electrode surface. Thus, formed SAM can potentially serve as sensor layer for various organic molecules such as pesticides, antibiotics, and optically active compounds.