Dense metallic membranes are primarily used for high-purity hydrogen separation from a mixture of gases, and especially hydrogen-permeable metallic membranes made of palladium-silver alloys being used for industrial application. However, palladium-silver alloy membranes have limited industrial application due to their high cost, and alternative to these and less expensive are non-palladium alloys. Vanadium-based alloy membranes are considered to be one of the most promising metallic membranes due to their higher permeabilities than palladium-silver and greater resistance to embrittlement as compared to pure vanadium. This paper will review metallic membranes permeation mechanism, V-based alloy membrane research status, the effect of catalyst layer on hydrogen-permeability, and vanadium-based alloy membrane fabrication.