Three new aliphatic thiol surfactants were synthesized by reacting alkyl bromide with hexamethyldisilathiane under a mild condition. This approach provides an easy access for the direct synthesis of various different length thiol surfactants which play a crucial role in tuning the properties of gold nanoparticles. Gold nanoparticles encapsulated with one of our synthetic thiols were prepared and well characterized by H NMR, UV-vis, FT-IR, and TEM. The hybrid nanoparticles are very stable in both organic solvents and the solid state.