When a clean glass surface is exposed to humid air, a thin water layer forms on the hydrophilic surface. Using ab initio molecular dynamics, we simulate the changes in the electronic structure of a CaO-Al2O3-SiO2 glass model upon vacuum fracture and subsequent exposure to H2O. When the glass is fractured, dangling bonds form, which lower the band gap of the surface by ∼1.8 eV compared to the bulk value due to mid-gap surface states. When H2O adsorbs onto the vacuum-fractured surface, the band gap increases to a value closer to that of the bulk band gap. Using two different hydroxylation methods, we find that the calculated band gap of the glass surface depends on the hydroxylation state. Surfaces with ∼4.5 OH/nm2 have smaller band gaps due to unfilled surface states, and surfaces with ∼2.5 OH/nm2 have larger band gaps with no apparent unfilled surface states. The resulting changes in the electronic structure, quantified by electron affinity and work function values, are hypothesized to play an important role in the electrostatic charge transfer based on the principles of surface state theory, which posit that the density of electronic surface states determines the amount of electronic charge transfer to or from material surfaces.