In this paper, a series of proton exchange membranes prepared by "Click Reaction" are reported. The cross-linked membranes are based on water soluble sulfonated poly (ether ether ketone) containing dipropenyl groups (SDPEEK-nE/nH). Compared with self-crosslinked membranes (SDPEEK-nS), this "Click" cross-linked membranes using 1,2-Ethanedithiol and 1,6-Hexanedithiol as the cross-linker exhibit extremely reduced water uptake and swelling ratio. The lowest proton conductivity at 80 degrees C of the "Click" cross-linked membranes reaches to 0.168 S cm(-1), and the highest methanol permeability of the "Click" cross-linked SDPEEK-8E is only 4.13 x 10(-7) cm(2) s(-1), which is 5 times lower than that of Nafion 117 membrane. All the results imply that the cross-linked membranes with novel thiol cross-linker are promising alternative material for fuel cell application. (C) 2013 Elsevier B.V. All rights reserved.