Combining molecular alignment with selective ion transport can increase the freedom to design ion-conducting polymeric materials and thus enhance applications such as battery electrolytes, fuel cells, and water purification. Here we employ pulsed-field-gradient (PFG) NMR diffusometry, H-2 NMR spectroscopy, polarized optical microscopy, and small-angle X-ray scattering to determine relations between counterion transport, dynamic coupling of water, and molecular alignment in aqueous solutions of a rigid rod sulfonated-aramid polyelectrolyte: poly(2,2'-disulfonyl-4,4'-benzidine terephthalamide) (PBDT). Na-23 PFG NMR on PBDT solutions and simple sodium solutions shows significantly slower Na+ counterion diffusion in PBDT, providing agreement between counterion condensation theory and quantitative transport information. Strikingly, from H-2 NMR spectroscopy we observe that the orientational order parameter of partially aligned solvent D2O molecules increases linearly with polymer Weight percentage over a large concentration range (1.4 to 20 wt %), while the polymer chains possess essentially a large and fixed order parameter S-matrix = 0.76 as observed using both SAXS and H-2 NMR on labeled polymers. Finally, we apply a two-state model of water dynamics and a physical lattice model to quantitatively relate D2O spectral splittings and nematic rod-rod distance. These studies promise to open new pathways to understand a range of anisotropic polymer systems including aligned polymer electrolyte membranes, wood composites, aligned hydrogels, liquid crystals, and stretched elastomers.