Ether-free poly(p-phenylene)-based anion exchange membrane materials with outstanding vanadium ion blocking properties are reported. The synthesized ionomers with a rigid backbone structure show small dimensional variations despite the high ion exchange capacities. Among the synthesized membranes, the QPPP-2 membrane with ion exchange capacity of 2.1 meq·g−1 exhibits high anion (OH−, SO4 2−, and Cl−) conductivity. The QPPP-2 membrane shows an extremely low diffusion coefficient (2.12 × 10−9 cm2 min−1) for VO2+, which is much lower than that of Nafion 115 (2.88 × 10−6 cm2 min−1), indicating the vanadium ion blocking property of QPPP-2. Moreover, the chemical and operational stabilities of the membranes are investigated via ex situ soaking tests in 0.1 M VO2 + solution and in situ operation tests for 100 cycles, respectively. The vanadium redox flow battery single cell assembled with the QPPP-2 membrane exhibits a coulombic efficiency of 99%, voltage efficiency of 87%, and energy efficiency of 86% during 100 cycles at 80 mA cm−2. The excellent chemical, morphological, and electrochemical properties of the QPPP-2 membrane make it suitable for use in vanadium redox flow battery.