Mobile devices in the next generation such as camera, cell phone, network, Note PC, etc. require higher power and energy sources due to convergences of various functions. Direct methanol fuel cell (DMFC) has been focused as an attractive power source, but there are critical issues involved in its commercialization with regard to the core technologies of materials, components, and system. The requirements of key technologies are differentiated from applications and fuel supply methods. Here, the roles of the proton-conducting membrane are discussed and the current status of DMFC systems is discussed in terms of proton conductivity, methanol permeability, and water management. Materials such as perfluorinated and partially fluorinated membranes, hydrocarbon membranes, composite membranes, and other modified ionomers have been studied. These would explain the critical issues of DMFC and the role of membranes for commercialization.