The orientation of water molecules on water bilayers is investigated on Cu(111) by a combination of scanning tunneling microscopy and density functional theory. Theory predicts that the application of a field reorients the adsorbed water molecules at a distance of close to a nanometer from the surface. Experimental evidence is presented for this prediction. Furthermore, the process differs strongly between adsorption on two and on three ordered layers. We propose that these results give insight into the behavior of the diffusive layer close to electrodes.