Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) is a powerful surface analysis tool. As an example, valuable details on the structure of water layers that form on oxidized silicon surfaces in humid environments have been extracted from this technique. Other work suggests that the structure of this interfacial water layer depends largely on the abundance of Lewis sites on the surface that can compete with interfacial water for hydrogen bonding partners. In this work, ATR-FTIR spectroscopy is employed to investigate the water structure that exists on a highly hydroxylated silica surface that is formed from the vapor-phase hydrolysis of silicon tetrachloride. Comparisons to native silicon oxide surfaces and water plasma treated silicon surfaces will be made, and implications for biomaterials science are discussed.