Enhancing the mass transport from the flow field side to the membrane side without sacrificing the active surface area is a critical strategy for the design of electrodes in flow-field structured vanadium redox flow batteries (VRFBs). In this work, we design and prepare a novel porous electrode with a gradient distribution in pores, enabling a gradual decrease in permeability but an increase in active surface areas from the flow field side to the membrane side. This design not only increases the electrode utilization due to the enhanced mass transport near the flow field side, but also avoids the loss of active surface area near the membrane side. Numerical modeling results show that compared to the conventional electrode design, the gradient electrode design can promote the uniform distribution of local reaction current density and overpotential, leading to a lower charge voltage and higher discharge voltage. Experimental results show that at the current density of 240 mA cm−2, the battery with the gradient electrode design delivers a 69% higher discharge capacity than that with the conventional electrode design, demonstrating the superiority of the gradient electrode design strategy.