Hypothesis: Water vapor binding to metal oxide surfaces produces thin water films with properties controlled by interactions with surface hydroxo sites. Hydrogen bonding populations vary across films and induce different molecular orientations than at the surface of liquid water. Identifying these differences can open possibilities for tailoring film-mediated catalytic reactions by choice of the supporting metal oxide substrate. Experiments: The (0001) face of a single sapphire (alpha-Al2O3) sample exposed to water vapor and the surface of liquid water were probed by polarization dependent Sum Frequency Generation-Vibration Spectroscopy (SFG-VS). Molecular dynamics (MD) provided insight into the hydrogen bond populations and molecular orientations across films and liquid water. Findings: SFG-VS revealed a submonolayer film on sapphire exposed to 43% relative humidity (R.H.), and a multilayer film at 78% R.H. Polarization dependent SFG-VS spectra showed that median tilt angles of free O-H bonds on the top of films are at similar to 43 degrees from the normal of the (0001) face but at 38 degrees on neat liquid water. These values align with MD simulations, which also show that up to 36% of all O-H bonds on films are free. This offers new means for understanding how interfacial reactions on sapphire-supported water films could contrast with those involving liquid water. (C) 2019 Elsevier Inc. All rights reserved.