In this article, an angle-resolved photoelectron spectroscopy (ARPES), X-ray absorption spectroscopy (XAS), anddensity-functional theory (DFT) investigations of water and ammonia adsorption on graphene/Ni(111) arepresented. The results of adsorption on graphene/Ni(111) obtained in this study reveal the existence of interfacestates, originating from the strong hybridization of the grapheneπand spin-polarized Ni 3dvalence band states.ARPES and XAS data of the H2O (NH3)/graphene/Ni(111) system give an information regarding the kind ofinteraction between the adsorbed molecules and the graphene on Ni(111). The presented experimental data arecompared with the results obtained in the framework of the DFT approach.