Electrochemical grafting of a water-insoluble diazonium salt in aqueous media onto an electrode surface was achieved by host-guest complexation. 1-(2-Bisthienyl)-4-aminobenzene (BTAB) was solubilized in a water/beta-cyclodextrin solution (beta-CD). The corresponding diazonium salt was generated in situ then electroreduced. This process leads to the attachment of bithiophene or short oligothiophene groups to the electrode surface. The modified surfaces were analyzed by cyclic voltammetry (CV), scanning electrochemical microscopy (SECM), X-ray photoelectron spectroscopy (XPS), infrared reflection absorption spectroscopy (IRRAS), and atomic force microscopy (AFM). The electrochemical investigations show that the water-based modified surface is similar to one generated in acetonitrile without beta-CD. Thus, the attached organic layer behaves like an electrochemical switch (above some threshold potential, a soluble external probe is oxidized, but the oxidized form cannot be reduced). The modified surfaces consist of grafted bisthienylbenzene (BTB) and cyclodextrins that can be removed from the surface. This procedure may be considered as a new means of creating a surface made of submicrometric holes in an organic semiconducting layer.