There has been a sustained research interest in the unique reactivities of ultra-small metal and metal oxide clusters. Numerous studies have highlighted the capability of the cluster deposition method to explore the catalytic reactivity of ultra-small clusters with different sizes, stoichiometries, and substrates. In this thesis, two beam line coupled surface analytical apparatus are introduced. The newly constructed one is an upgraded version of the previous one with better mass selection capability and improved geometries for combined temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS) analysis. Two combined TPD and XPS studies, which were performed on the previous apparatus, are presented, including ligation and decomposition of 1,6-hexanedithiol, and decomposition of dimethyl methylphosphonate (DMMP) by size selected copper and copper oxide clusters. Several crucial troubleshooting processes for the new apparatus are discussed, and some preliminary experimental results are presented
