We have studied the morphology of a novel series of benzimidazole-based ionenes, methylated poly(hexamethyl-p-terphenylbenzimidazolium) (HMT-PMBI), in halide form. Materials with anion-exchange capacities ranging from 0 to 2.5 mequiv/g were studied. X-ray scattering reveals three length scales in the materials: ion-polymer spacing (4 Å), polymer-polymer interchain spacing (6 Å), and an intrachain repeat distance (20 Å). No long-range structure is apparent above the monomer length, which is rare in ion-conducting polymer membranes. In preliminary molecular dynamics simulations, water molecules were observed forming chains between ions, even at a modest level of hydration, providing an interpenetrating network where conductivity can occur.