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We have developed a novel poly(ether imide)‐based alkaline anion‐exchange membrane. The effects of several important parameters on the chloromethylation of the membrane have been investigated. These parameters include the reaction temperature, reaction time, concentration of the chloromethylation agent, concentration of the polymer, and amount of the catalyst. The results show that all the studied parameters have significant impacts on chloromethylation. Among them, the concentration of the chloromethylation agent plays a key role in increasing the attachment of chloromethyl functional groups onto the polymer. It ha been found that gelation can be avoided if these reaction parameters are controlled. This study also provides useful information for the successful chloromethylation of other membrane‐related polymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009