We present valence photoelectron emission spectra of liquid water in comparison with gas-phase water, ice close to the melting point, low temperature amorphous and crystalline ice. All aggregation states have major electronic structure changes relative to the free molecule, with rehybridization and development of bonding and anti-bonding states accompanying the hydrogen bond formation. Sensitivity to the local structural order, most prominent in the shape and splitting of the occupied 3a(1) orbital, is understood from the electronic structure averaging over various geometrical structures, and reflects the local nature of the orbital interaction. (C) 2008 Elsevier B. V. All rights reserved.