The VB group (Nb, V, Ta) refractory metals have higher hydrogen permeability and lower price than commercial Pd, so they have become a new generation of preferred hydrogen separation membrane materials to replace palladium. In order to prepare high flux hydrogen separation alloy film on a large scale, the ingot alloy was first cold rolled to obtain large size flat film, and then the flux efficiency of alloy film was improved by annealing treatment to improve permeability. In this paper, the research progress of cold rolling formability, rolling and subsequent annealing microstructure evolution and hydrogen permeability of alloys are reviewed, the composition effect of cold rolling film formation is analyzed, and the relationship between microstructure and permeability of cast, cold rolling and annealing alloys is described. The problems of developing high flux hydrogen separation alloy membranes by rolling subsequent annealing to improve the microstructure were discussed. Finally, the prospect of cold rolling and subsequent annealing to realize the large-scale production of low thickness and high permeability hydrogen separation alloy membranes at low cost was prospected.