Abstract: The excellent characteristics of the direct methanol fuel cell (DMFC) have made it the subject of much research in recent years. The principal component influencing the performance of the DMFC is proton exchange membrane. In this paper，recent research progress of the membrane is reviewed，including the development of natural macromolecules used as proton exchange membranes. The advantages，disadvantages and promising applications of this kind of material in the DMFC are also discussed.