Comb-shaped polysulfone copolymers were synthesized by the click reaction, copper(I) catalyzed azide-alkyne 1,3-dipolar cycloaddition, using polysulfone having azidomethyl side group (PSf-N-3) and sulfonated polytriazole having one ethynyl chain-end group. PSf-N-3 was prepared by the substitution reaction of polysulfone through chloromethylation followed by azidation, and sulfonated polytriazoles having one ethynyl chain-end group was synthesized via the click reaction using 1,4-diethynylbenzene and 4,4'-diazido-2,2'-stilbenedisulfonic acid disodium salt tetrahydrate with CuI followed by end-capping process. Tough, flexible, and transparent membranes could be prepared by solution casting from the comb-shaped polysulfone copolymers and ion exchange capacity (IEC) of the resulting membranes could be controlled by changing the chain length of the sulfonated polytriazoles. The comb-shaped polysulfone membranes showed enhanced physicochemical stability and significantly higher proton conductivity when compared with a sulfonated poly(arylene ether sulfone) (SPAES) membrane having a similar IEC due to the distinct hydrophilic-hydrophobic phase separated morphology. The fuel cell performance of membrane electrode assembly with the comb-shaped polysulfone membrane is superior to those with the SPAES and Nafion-212 membranes at the various operating conditions.