Common issues aqueous-based vanadium redox flow batteries (VRFBs) face include low cell voltage due to water electrolysis side reactions and highly corrosive and environmentally unfriendly electrolytes (3 to 5 M sulfuric acid). Therefore, this investigation looks into the comparison of a highly conductive ionic liquid with a well-studied deep eutectic solvent (DES) as electrolytes for non-aqueous VRFBs. The latter solvent gives 50% higher efficiency and capacity utilization than the former. These figures of merit increase by 10% when nitrogen-doped graphene (N-G)-modified carbon papers, via a one-step binder-free electrophoretic deposition process, are used as electrodes. X-ray computed tomography confirms the enhancement of electrochemical surface area of the carbon electrodes due to N-G while electrochemical impedance spectra show the effect of its higher conductivity on improving RFB performance. Finally, potential strategies for the scaling-up of DES-based VRFBs using a simple economical model are also briefly discussed. From this study, it is deduced that more investigations on applying DESs as non-aqueous electrolytes to replace the commonly used acetonitrile may be a positive step forward because DESs are not only cheaper but also safer to handle, far less toxic, non-flammable, and less volatile than acetonitrile.