Langmuir-Blodgett (LB) deposition of thiol-stabilized gold clusters is reported to be controllable through the action of a hydrophilic thiol in the subphase, leading to reproducible monolayer transfer. The Figure is a schematic representation of a gold cluster, denoted Au55SiOS and prepared from a precursor by ligand exchange with a oligosilsesquioxane-based thiol derivative, with 12 thiol molecules in the ligand shell.