Utilizing scanning tunneling microscopy, we have explored the self-assembling and electronic properties of unsymmetrical disulfides CH3(CH2)(n)SS(CH2)(n+1)NC60 (where n = 5 or 10, and C-60 = buckminster-fullerene) adsorbed onto Au(111). We analyzed self-assembled monolayers (SAMs) derived from the fullerene disulfides as well as SAMs formed by the insertion of the disulfides into self-assembled alkanethiol monolayers. By studying various combinations of fullerene disulfides and alkanethiols, we found that the degree of insertion is governed primarily by the chain length of the C60 tether relative to the surrounding alkanethiol matrix. In addition, we used the insertion technique to probe the electronic properties of the tethered fullerenes as a function of alkyl chain length.