On the surface of mesoporous silica thin films (MSTF) which were fabricated by sol-gel approach there are existences of water and three different silanol types including chained, germinal and isolated silanol. Their amounts changes as a function of aging time of used sol solution, as confirmed by FT-IR. The adsorbed water generates ionic carriers such as H+ and OH- and passivates the Si dangling bonds at the interface of silicon wafer-MSTF. The ionic carriers can not only transport across the thickness of thin film to enhance the leakage current but also diffuse toward the silicon wafer-MSTF interface to depassivate Si dangling bonds. On the other hand, chained silanols or germinal silanols promote the moisture adsorption of MSTF and tend to form strongly hydrogen bonded systems with adsorbed water molecules resulting in very high dielectric constant. Isolated silanol, on the contrary, affects less on electrical properties of thin film.