Charge redistribution at graphene/dielectric interfaces is predicated upon the relative positioning of the graphene Fermi level and the charge neutralization level of the dielectric. The authors present an angle-resolved near-edge x-ray absorption fine structure (NEXAFS) spectroscopy investigation of single-layered graphene transferred to 300 nm SiO2/Si with subsequent deposition of ultrathin high-κ dielectric layers to form graphene/dielectric interfaces. The authors’ NEXAFS studies indicate the appearance of a distinct pre-edge absorption for graphene/HfO2 heterostructures (but not for comparable TiO2 and ZrO2 constructs). The hole doping of graphene with substantial redistribution of electron density to the interfacial region is proposed as the origin of the pre-edge feature as electron depletion renders part of the initially occupied density of states accessible for observation via NEXAFS spectroscopy. The spectral assignment is validated by calculating the NEXAFS spectra of electron- and hole-doped graphene using density functional theory. In contrast, a similarly sputtered metallic TiN layer shows substantial covalent interfacial hybridization with graphene.