Chemical cross-linking anion exchange series membranes were prepared from linear engineering plastics poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) by conducting the processes of bromination and amination at both benzyl and aryl positions. Compared with the traditional technologies, the membrane route described in this paper has cancelled the chloromethylation process and thus, given up the use of chloromethyl methyl ether, which has been considered as a potential harmful toxicity material. The ion exchange capacity, water content, membrane potential and transport number of membranes were studied. The results show that the membrane properties are significantly affected by the bromination processes benzyl-substitution will enhance the ion exchange capacity and water content, while the aryl-substitution will decrease the water content with approximately unchanged ion exchange capacity. By properly balancing them, a series of membranes can be obtained to comply with different industrial requirements, such as diffusional dialysis, electrodialysis, and water splitting processes.