It is an important research topic to construct microphase separation in anion exchange membranes (AEMs). The integration of rigid anthracene units into the main chains to form poly(anthracene-co-p-terphenyl piperidinium) AEMs is a new method by using π-π stacking to regulate microphase separation and construct ion transport channels in membranes. In this study, anthracene units were introduced for the first time to prepare AEMs with different anthracene contents. It is found that the introduction of rigid anthracene units into the backbone leads to an increase in the fractional free volume (FFV) of the membranes and a decrease in the ion conductive resistance. Moreover, the existence of long flexible di-piperidinium side chain helps to adjust the rigidity of the AEMs and enhances the mechanical properties of the membrane. The ionic conductivity of PA10TP-DMP is 153.8 mS cm−1 (80 °C). In the meanwhile, the conductivity retention of 91.7% was observed after the alkaline resistance test (80 °C, 2 M NaOH) for 1200 h. In addition, the PA10TP-DMP based H2-O2 single cell has a peak power density of 840.3 mW cm−2 and a high durability after 100 h test.