Self-assembled monolayer films of (3-mercaptopropyl)trimethoxysilane (3MPT) and their hydrolysis products on Ag and Au surfaces are characterized using Raman spectroscopy, FTIR spectroscopy, ellipsometry, X-ray photoelectron spectroscopy (XPS), and electrochemistry. 3MPT monolayers are formed through metal-thiolate bonding through the S atom on both metals, similar to other alkanethiol chemisorption chemistries. The orientation of 3MPT molecules in these monolayers is similar on both metals. Prior to hydrolysis, the molecules form an organized monolayer with the methoxy headgroups oriented largely parallel to the surface and the propyl chain in a largely trans conformation. When the methoxy groups are hydrolyzed, the 3MPT molecules cross-link through the formation of siloxane bonds. Although the surface vibrational spectroscopy indicates the presence of a small number of unreacted silanol groups on the siloxane surface, cyclic voltammetry of underpotential deposition of Pb suggests that the Si-O-Si network is highly cross-linked and relatively free from gross defects. The number of these unreacted silanols is estimated using XPS to be fewer than 5% of the original Si-O sites in the 3MPT monolayer.