New alpha,omega-semifluorinated dithiols HS-(CH2)(11)-(CF2)(n)-(CH2)(11)-SH, called DTn, and corresponding dithioacetate molecules CH3COS-(CH2)(11)-(CF2)(n)-(CH2)(11)-SCOCH3, called DTAn (n = 4,6,8), were synthesized and used to create self-assembled monolayers (SAMs) on both untreated copper surfaces and electrochemically reduced ones. The aim of this study is to assess the organization of the resulting SAMs, particularly the effect of the presence of two perhydrogenated segments surrounding the perfluorinated one, and the ability of these difunctional molecules to bind copper substrates by only one end per molecule. In each case, the organization of the SAM is rather poor and only DTA8 molecules seem to adopt an upright position on reduced copper. In addition, the layers have been investigated by cyclic voltammetry (CV) to assess their coverage. DT4 SAMs reveal a covering ratio higher than 99%.