The present invention discloses a poly(oxadiazole aryl ether-co-bisphenol fluorine) proton exchange membrane and a preparation method thereof. The proton exchange membrane is obtained by one step; specifically: mixing and reacting a base polymer obtained from a decafluorobenzadiazole and bisphenol fluorine copolymer with a functionalized reagent and forming a membrane to obtain the proton exchange membrane. The reaction with the functionalized reagent is primarily realized via nucleophilic aromatic substitution. The proton exchange membrane obtained by the present invention has a high ion conductivity; at 30°C the conductivity is 58 mS·cm-1, and at 70°C it reaches 137 mS·cm-1. Further, the proton exchange membrane has strong mechanical properties and a low methanol permeability, the methanol permeability being less than half that of a Nafion® 117 membrane. Upon assembling the membrane in a direct methanol fuel cell and testing, results showed that at 90°C, the maximum power of the cell was 75 mW·cm-2, and at 100°C, the maximum power reached 85 mW·cm-2.
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