The overall electronic structure of a water/semiconductor interface is studied for the first time by nb initio molecular dynamics for realistic solvent configurations. The present study expands on our earlier work [J. Chem. Phys. 103, 7569 (1996)] by including a complete nb initio description of the surface and the solvent. Several statistically independent solvent configurations are generated via classical molecular dynamics as a starting point for a realistic sampling of the true solvent electronic structure via ab initio dynamics. A significant degree of mixing is observed between semiconductor electronic surface states and the bulk water orbitals. A new method is also given to facilitate the use of gradient corrected density functionals with Vanderbilt pseudopotentials.