Anion exchange membrane fuel cells (AEMFCs) have been developed as promising energy conversion devices for stationary and mobile applications due to their potentially low cost. To realize high-performance AEMFCs, new polymeric membranes are needed that are highly conductive and chemically stable. Here we report a systematic study of anion exchange membranes (AEMs) with multiple cations per side chain site to demonstrate how this motif can boost both the conductivity and stability of poly(2,6-dimethyl-1,4-phenylene oxide)-based AEMs. The highest conductivity, up to 99 mS/cm at room temperature, was observed for a triple-cation side chain AEM with 5 or 6 methylene groups between cations. This conductivity was considerably higher than AEM samples based on benzyltrimethylammonium or benzyldimethylhexylammonium groups with only one cation per side chain site. In addition to high conductivity, the multication side chain AEMs showed good alkaline and dimensional stabilities. High retention of ion exchange capacity (IEC) (93% retention) and ionic conductivity (90% retention) were observed for the triple-cation side chain AEMs in degradation testing under 1 M NaOH at 80 °C for 500 h. Based on the high-performance triple-cation side chain AEM, a Pt-catalyzed fuel cell with a peak power density of 364 mW/cm2 was achieved at 60 °C under 100% related humidity.