A new type of host adsorbates has been developed which possess a resorcin[4]arene headgroup with four di-n-decyl sulfide chains underneath. Self-assembled monolayers of these adsorbates with various functionalities at the head groups, i.e., methylene ether (the so-called cavitand), methyl ether, 2-fluoroethyl, hydroxyl, N-propylacetamide, and several carboxyl esters, on gold were characterized with polarized infrared external reflectance spectroscopy (PIERS), X-ray photoelectron spectroscopy (XPS), surface plasmon spectroscopy (SPS), and contact angle and electrochemical measurements. Highly organized monolayers are formed from 1 mM solution at 60 degrees C by adsorbates that have headgroups smaller or equal to the cross-sectional area occupied by the eight alkyl chains underneath (less than or equal to 160 Angstrom(2)).