The transport properties of membranes used in vanadium redox flow batteries (VRFB) are fundamental in battery performance. High proton conductivity and low vanadium ion permeability must be achieved to achieve high battery performance. However, there is a trade-off relationship between proton conductivity and vanadium ion permeability. So, solving this trade-off relationship is crucial in VRFB development. Also, maintaining high coulombic efficiency, voltage efficiency, and energy efficiency is essential for high-performing VRFB. Recently, various attempts have been made, primarily on composite membranes and SPEEK membranes, to overcome the existing limit of Nafion membranes. VRFB is an essential class of rechargeable battery in composite membranes reviewed here.