High molecular weight, quaternary ammonium-tethered poly(biphenyl alkylene)s without alkaline labile C-O bonds were synthesized via acid-catalyzed polycondensation reactions for the first time. Ion-exchange capacity was conveniently controlled by adjusting the feed ratio of two ketone monomers in the polymerization. The resultant anion exchange membranes showed high hydroxide ion conductivity up to 120 mS/cm and excellent alkaline stability at 80 °C. This study provides a new synthetic strategy for the preparation of anion exchange membranes with robust fuel cell performance and excellent stability.