with various functional nanomaterials offering synergic properties, such as metal oxides, [5] conducting polymers [2] or carbon materials. [6][7][8][9][10][11][12] The combination of carbon materials with ZnO offers the benefits of both the electrical double layer (EDL) capacitance of the carbon materials with large specific surface area (SSA) and the faradaic contribution of the ZnO, thereby optimizing the electrochemical performance of the ZnO-based SCs. [8] Among carbon materials, graphene has spurred significant interest in electrochemical energy storage due to its high SSA, superior electronic conductivity and chemical resilience. [13][14][15] Therefore, an integration of 1D ZnO nanostructures and graphene is desirable for electrode materials. Besides, the rational design and synthesis of 1D ZnO and graphene nanostructures with a 3D interconnected morphology is another consideration for a promising SC device. Compared with the ZnO nanostructures grown on the graphene, where only upper graphene surface is available to electrolyte, a thin layer of graphene covered ZnO nanostructures is postulated to provide higher number of electroactive sites for charge storage due to the accessibility of both surfaces (upper and lower) to electrolyte, allowing for more effective charge and mass exchange. However, this unique ZnO/graphene heterostructure has rarely been studied, and rare examples include the reduced graphene oxide (rGO)/ZnO nanorods composites synthesized on graphene coated poly(ethylene terephthalate) (PET) flexible substrates, leading to the rGO/ZnO/rGO sandwich structures [16,17] and 3D ZnO (zinc oxide)/rGO/ZnO structures where the ZnO nanostructures are sandwiched or intercalated between the graphene sheets. [3] However, fundamental importance of the ionic flux into the electrode, which plays an essential role in understanding the charge-storage mechanism of a specific electrochemical system is generally underestimated. The study of such architectures with coupled methods such as coupling electrochemistry with gravimetric analysis, i.e., quartz crystal microbalance (QCM) can significantly contribute to their further development.Electrochemical quartz crystal microbalance (EQCM) has developed into a powerful in situ technique to measure ionic fluxes in different electrochemical systems, [18][19][20][21][22][23][24] in which not only the current response (ΔI) but also the in situ capturing of global gravimetric change (Δm) at the electrode/electrolyte interface is The present work is on the synthesis and characterization of vertically aligned ZnO nanostructures sheltered by electrochemically reduced graphene oxide (ERGO), i.e., ZnO@ERGO, which are directly generated on quartz resonators of microbalance sensors. The vertical orientation of the ZnO nanorods is achieved by a two-step synthesis method involving an electrochemically grown seed layer and a subsequent hydrothermal growth. Deposited ERGO thin layer turns out to be highly effective to enhance the electrochemical performances of vertically oriented Z...