has been a turning point in the study and application of 2D materials. In this sense, the very high ballistic transport distances of the order of the micron and very large carrier mobility [2][3][4] combined with the absorption of 2.3% of visible light, [5] places graphene as an extraordinary candidate for new optoelectronic devices. On the other hand, graphene's impermeability to most gases [6] makes it also a promising candidate for ultrathin passivation coating. [7] However, this idealistic view contrasts with the reduced number of real applications to industry and/or produced mass electronic devices. Without doubt, this frustrating fact is related to the difficulty to grow large areas of non-defective graphene, but also with the complexity of the interaction of graphene with other materials (substrates, multilayer systems) and/or media (gas, liquids) in contact with it, which leads to changes of the graphene properties.Focusing on this last point, the substrate plays a very important role in the electronic properties of graphene due to the strength of the bonding between both. As Weatherup et al. summarized, [7] depending on the position of the d valence band states with respect to the Fermi level, [8] two different interactions are reported for metallic substrates. In the case of Ni, Co, Fe, or Pd, the strong hybridization between π graphene states and metal d states leads to the destruction of the linear dispersion of graphene at the K point. For weak interactions, such as Cu, Au, Ag, and Pt, this linear dispersion is preserved but charge transfer between metal and graphene normally shifts the Fermi level position, leading to doping of graphene. Moreover, for SiC (0001) a covalent bonding between the substrate and the first carbon layer also prevents good electrical properties of graphene. [9,10] In all these cases, this interaction can be modulated or suppressed by controlled intercalation of metallic atoms at high temperatures, [11,12] or even at room temperature for alkaline elements. [13,14] The formation of an oxidized layer between substrate and graphene [15,16] can also decouple graphene from substrates.Nevertheless, the last description offers again a simplified view of the problem. The majority of the experimental and This study presents experimental data of the interactions and reactions that occur during the early stages of the growth of ZnO on graphene supported on polycrystalline copper and the subsequent changes on the electronic properties of the graphene. The combination of substrate, graphene, and intercalated species (such as oxygen and water molecules) between graphene and copper due to air exposure, together to the evaporation of metallic zinc under oxygen atmosphere, induces the electronic decoupling of the graphene from copper by the formation of a nanometric layer of copper oxide. In particular, the final stage consists in the formation of a complex interface formed by ZnO/ZnO 1−x /Zn/G/Cu 2 O/Cu. The role of each actor is discussed in terms of a galvanic corrosion reaction of the met...