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Like batteries, fuel cells provide an inherently clean source of energy with no adverse environmental impact during operation. The utilization of methanol as a fuel is advantageous: it has an energy density of about 6 kWh/kg, which is, much higher than that of other commercialized batteries. This review is focused on the core of a DMFC, i.e., the symmetric membrane, in particular on the block copolymers used for its preparation as an alternative to well-known Nafion. The synthesis of block copolymer ionomers based on different building block types, with special emphasis on the critical issue of methanol permeability and proton/methanol selectivity, as well as the effect of block length and crosslinking are described and discussed.