We designed multivalent β-cyclodextrin-based adsorbates bearing different anchoring groups aiming to yield stable monolayers with improved packing and close contact of the cavity to the gold surface. Toward this end the primary rim of the β-cyclodextrin was decorated with several functional groups, namely iodide, nitrile, amine, isothiocyanate, methyl sulfide, and isocyanide. Monolayers formed by these adsorbates were characterized by contact angle measurements, surface plasmon resonance spectroscopy, polarization modulation infrared reflection adsorption spectroscopy, X-ray photoelectron spectroscopy, and electrochemistry. The nature of the anchoring group influenced the adsorption kinetics, thickness, layer stability, number of anchoring groups bounded to the surface, and packing in the resulting monolayers. Therefore, chemical manipulation of multivalent adsorbates can be used to modify the properties of their monolayers.