Ambient pressure x-ray photoelectron spectroscopy (AP-XPS) supported by density functional theory (DFT) calculations was used to characterize the interaction of water with two-dimensional (2D) silica and aluminosilicate bilayers on Pd(111). Starting with oxygen adsorbed at the SiO2/Pd interface, exposure to water caused the SiO2-derived XPS peaks to shift to higher binding energy and the removal of an O 1s feature associated with interfacial adsorbed oxygen. These observations were attributed to the formation of a mixed water-hydroxyl interface, which eliminates the interfacial dipolar layer, and its associated electrostatic potential, created by adsorbed oxygen. Interfacial oxygen also reacted with H2 to produce adsorbed water which also caused an upward binding energy shift of the SiO2 peaks. Spectra recorded under 0.5 Torr water revealed additional water adsorption and a further shift of the overlayer peaks to higher binding energy. Incorporating Al into the 2D material caused the bilayer peaks to shift to lower binding energy which could be explained by electron donation from the metal to the bilayer. Although the stronger interaction between the bilayer and Pd substrate should restrict interfacial adsorption and reaction, similar trends were observed for water and hydrogen exposure to interfacial adsorbed oxygen. Less water adsorption was observed at the aluminosilicate interface which is a consequence of Al strengthening the bond to the metal substrate. The results reveal how the sensitivity of XPS to interfacial dipoles can be exploited to distinguish reactions taking place in confined spaces under 2D layers and how tuning the composition of the 2D layer can impact such reactions.