To explore the intrinsic correlation between the rigidity and distortion degree of polymer backbones and the diffusion dialysis (DD) performance of anion exchange membranes (AEMs), pyrrolidinium-functionalized poly(arylene ether sulfone)s containing different Cardo (TPM) moieties were prepared. The structures, properties and DD performance of above AEMs were systematically evaluated. As the Cardo (TPM) group angle increased, the d-spacing, fractional free volume, and membrane area resistance increased, and the microphase separation structures, hydrophilicity, and acid flux decreased, mainly because larger Cardo (TPM) group angles are unfavourable for the close packing of polymer chains in space. Both the Cardo-type and TPM-type AEMs exhibited universal ultrahigh H+/Fe2+ selectivity (S > 3819), which was mainly attributed to the synergistic influence of their rigid narrow ion transport channels, small pore diameter (0.48–0.62 nm) and narrow pore size distribution (0.24–0.68 Å). Additionally, due to the high-density amide groups of TPM units, which decreased the hydrophobicity of the polymer skeleton and induced the formation of an additional transport pathway for Fe2+ through hydrogen bonding interactions, the TPM-type AEMs showed both lower acid flux and selectivity, suggesting that the structure of hydrophilic auxiliary groups should be carefully designed when improving the DD performance of AEMs. Display omitted •AEMs based on pyrrolidinium functionalized Cardo (TPM) poly(arylene ether sulfone)s were prepared.•The structures, properties, and DD performance of prepared AEMs were evaluated.•The correlations between Cardo (TPM) groups and the DD performance were revealed.