Single and multicomponent mixed layers of silsesquioxane clusters on freshly evaporated gold surfaces have been investigated by X-ray photoelectron spectroscopy and reflection-absorption infrared spectroscopy. Approximately 5-10% of the cluster layers (e.g., H8Si8O12 and H10Si10O15) on gold desorb upon evacuation of the adsorbate from the reaction chamber. These open adsorption sites are an avenue for cluster displacement reactions that yield mixed monolayers (e.g., H8Si8O12/D8Si8O12 and H8Si8O12/C6H13-H7Si8O12) of several compositions on gold. This dynamic behavior is not observed for the C6H13-H7Si8O12 cluster layer on gold. Rather, this molecule acts as a poison to these reported displacement processes at the gold surface.