Langmuir-Blodgett films of octadecylmercaptan (ODM) were formed on an aqueous subphase and transferred to gold substrates under electrochemical potential control by means of a modified LB Balance. The monolayers were investigated by surface analytical techniques (XPS, ARXPS, AES, IRRAS) and by electrochemical methods (cyclic voltammetry, impedance spectroscopy). The results are compared to self-assembled films (SA) of ODM on gold.