Two strategies for improving the electroactivity towards VO 2 + / VO 2 + redox pair, the limiting process in all-vanadium redox flow batteries (VFBs), were presented. CuPt3 nanoparticles supported onto graphene substrate and nitrogen and oxygen polyacrylonitrile (PAN)-functionalized electrodes materials have been evaluated. The morphology, composition, electrochemical properties of all electrodes prepared was characterized with field emission-scanning electrode microscopy, X-ray photoelectron spectroscopy, cyclic voltammetry, electrochemical impedance spectroscopy and cell charge–discharge test. The presence of the CuPt3 nanocubes and nitrogen and oxygen functionalities enhance the electrocatalytic activity of the electrodes materials accelerating the oxygen and electron transfer processes. The battery performance was also evaluated using PAN-functionalized electrodes exhibiting a high of energy efficiency of 84% (at current density 20mAcm−2) up to 30th cycle, indicating a promising alternative for improving the VFB.