A polyelectrolyte containing a sulfonium cation, poly(methylsulfonio-1,4-phenylenethio-1,4-phenylene trifluoromethanesulfonate) (1) was tested as a separator in a zinc–air cell. In comparison with the commercially available separators such as polypropylene, polysulfonium 1 was highly effective to prevent cation permeation from the anode to cathode and effectively increased the capacity six-fold greater than that of polypropylene during discharge. This phenomenon was explained by the ion-exchange process of the membrane 1, which showed an anion-permselectivity toward OH− at low KOH aqueous solution concentrations (<1M).