Development of the Vanadium Redox Flow Battery (VRFB) has been widely reported but typically only focuses on one part of the cell (e.g. electrode, electrolyte, or membrane). Improvement to a single part of the cell may cause side effects on other parts during long-term cycling leading to an overall drop in the performance of the battery. To avoid this, the use of nanofluidic electrolyte seems to be a promising approach to enhance the performance of both electrode and electrolyte simultaneously. This paper aims to investigate the electrochemical performance of a newly prepared reduced graphene oxide (rGO) nanofluidic vanadium electrolyte, applicable for Vanadium Redox Flow Batteries (VRFB). Herein, we report for the first time a stable rGO/vanadium nanofluidic electrolyte with improved electrochemical performance. Benefiting from the low degree of oxidation as compared to GO, the rGO can provide high electrical conduction due to the presence of sufficient functional groups, which can facilitate the redox reactions. The effect of various concentrations of rGO on the electrochemical performance is investigated. The current collector (carbon cloth (CC) electrode) was further characterized using different physico-chemical techniques to underpin the stability of rGO nanofluids. The results suggested that the electrochemical performance of vanadium electrolyte increases with the concentration of rGO. Improvements of approx. 15% to 20% were achieved in peak potential separation and current density rates, respectively. In addition, the incorporation of rGO in nanofluidic electrolyte significantly decreases the electrolyte and charge transfer resistance by ∼10% and ∼99%, respectively, and improves the vanadium ion diffusion process by ∼50%.