The synthesis of a new type of host adsorbate possessing a large resorcin[4]arene headgroup and four di-n-decyl sulfide chains underneath is described. The cross-sectional area of the alkyl chains is equal or larger than that of the headgroups which makes these resorcin[4]arene tetrasulfides suitable for self-assembly onto gold surfaces to form well-packed monolayers of which the outer interface is composed of receptor sites and the alkyl chains underneath the cavity headgroups passivate the gold surface. Resorcin[4]arene tetrasulfides with the following functionalities at the resorcin[4]arene headgroup were synthesized: methylene ether (the so-called cavitand), methyl ether, 2-fluoroethyl, several carboxyl esters, N-propylacetamide and hydroxy.