The interactions of glycine (Gly) with amorphous solid water (ASW) nanolayers (≤100ML), vapor-deposited on single crystalline AlO x surfaces at 100K, have been investigated by near-edge X-ray absorption fine structure spectroscopy (NEXAFS) at the oxygen K-edge, temperature-programmed thermal desorption (TPD), X-ray photoelectron spectroscopy (XPS), and temperature-dependent work function measurements. Gly-on-ASW, ASW-on-Gly, and Gly on top of ASW-on-Gly ultrathin films have been fabricated. In contrast to the uniform ASW films grown directly on the hydrophilic AlO x , water molecules adsorb on the hydrophobic Gly films in the form of 3D ASW clusters. This leads to significant differences in the NEXAFS and work function data obtained from ASW-on-AlO x and ASW-on-Gly films, respectively. Furthermore, these structural differences influence the chemical state of Gly molecules (neutral vs. zwitterionic) adsorbed on top of ASW films. N1s XPS measurements revealed an increased amount of neutral Gly molecules in the film top-deposited on the ASW-on-Gly structure in comparison to the neutral Gly in the films directly condensed on AlO x or grown on the ASW substrate. H 2 O TPD spectra demonstrate that the crystallization and desorption processes of ASW are affected in a different way by the Gly layers, top-deposited on to ASW-on-AlO x and ASW-on-Gly films. At the same time, Gly adlayers sink into the ASW film during crystallization/desorption of the latter and land softly on the alumina surface in the form of zwitterionic clusters.