The effect of the distance between a β-cyclodextrin (βCD) host core and a conductive substrate on the electron-transfer rate of complexed guests as well as of free-diffusing electrochemically active probes has been studied. First we have evaluated a set of short-tethered βCD adsorbates bearing different anchoring groups in order to get a reliable platform for the study of short-distance electron transfer. An electrochemically active trivalent guest was immobilized on these host monolayers in a selective and reversible manner, providing information about the packing density. Iodine- and nitrile-functionalized βCD monolayers gave coverages close to maximum packing. Electron transfer in the presence of Fe(CN)6 3-/4- studied by impedance spectroscopy revealed that the electron transfer of the diffusing probe was 3 orders of magnitude faster than when the βCD cores were separated from the surface by undecyl chains. When an electrochemically active guest was immobilized on the surface, electron-transfer rate measurements by cyclic voltammetry and capacitance spectroscopy showed differences of up to a factor of 8 for different βCD monolayers. These results suggest that increasing the distance between the βCD core and the underlying conductive substrate leads to a diminishing of the electron-transfer rate.