Polymer electrolyte membrane (PEM) is a key material that strongly affects the cell performance, cost and application prospect of the PEM fuel cell. The membrane acts as a separator to prevent mixing of the reactant gases and as an electrolyte for proton transportation. Radiation-grafted PEM has a special chemical structure, composing of fluorinated main chains and sulfonated side chains. The main chain acts as a stable backbone that gives the necessary strength, dimensional stability and gas barrier while the side chain gives the ability of proton transportation. In our study, the suitability of some base films, monomers and crosslinkers, as well as the preparation processes have been investigated in detail in order to develop a high performance radiation-grafted PEM.