<p>The Vanadium redox flow batteries (VRFBs) have been considered one of the most promising large-scale energy storage technologies. However, the bottleneck constraining the development of their electrodes lies in the low energy efficiency at high current densities. In order to reduce the electrochemical polarization of electrode materials and improve the power density of VRFBs, we propose a strategy for growing porous metal–organic framework (MOF-5) on graphene oxide (GO) carbon-based materials with polydopamine (PDA) as a chemical N-doping anchoring agent, and the fabricated high-stability conductive carbon network structure MOF-5/rGO/PDA is used as an anode electrode material for VRFBs to modify blank carbon felt (CF). The electrochemical test results show that the improved active sites accelerated the redox reaction rate of vanadium ions, enabling the MOF-5/rGO/PDA composite electrode material to exhibit excellent electrocatalytic activity, and effectively improve the voltage efficiency (VE) and energy efficiency (EE) of the VRFBs. Compared with the original blank CF electrode, the MOF-5/rGO/PDA composite–modified electrode shows a VE enhancement of 10.8% and an EE enhancement of 11.7% at a current density of 100 mA cm⁻². In addition, the specific capacity of the modified electrode increases by 64.4% at 120 mA cm⁻², while at 140 mA cm⁻² the EE of the modified electrode can still reach 79%. It is proved that the chemical N doping introduced by –NH₂ groups in PDA further improves the conductivity of the composite electrode material, and the selective reduction of GO by PDA and the chelation with MOF-5 jointly promote the construction of a stable carbon network, which can effectively prevent electrode fracture. This work provides a new idea for advancing the further application of VRFBs.</p> Graphical Abstract <p></p>