<p>While being a promising candidate for large-scale energy storage, the current market penetration of vanadium redox flow batteries (VRFBs) is still limited by several challenges. As one of the key components in VRFBs, a membrane is employed to separate the catholyte and anolyte to prevent the vanadium ions from cross-mixing while allowing the proton conduction to maintain charge balance in the system during operation. To overcome the weakness of commercial membranes, various types of membranes, ranging from ion exchange membranes with diverse functional groups to non-ionic porous membranes, have been designed and reported to achieve higher ionic conductivity while maintaining low vanadium ion permeability, thus enhancing efficiency. In addition, besides overall efficiency, stability and cost-effectiveness of the membrane are also critical aspects that determine the practical applicability of the membranes and thus VRFBs. In this article, we have offered comprehensive insights into the mechanism of ion transportation in membranes of VRFBs that contribute to the challenges and issues of VRFB applications. We have further discussed optimal strategies for solving the trade-off between the membrane efficiency and its durability in VRFB applications. The development of state-of-the-art membranes through various material and structure engineering is demonstrated to reveal the relationship of properties-structure-performance.</p>