We present all atom explicit water Molecular Dynamics simulation results for the structure of short (six monomer units) aliphatic ionenes in mixtures with a low-molecular weight electrolyte. The SPC/E model was used to describe water. Long-range effects were taken into account via the Ewald summation procedure. The results indicate that strongly hydrated ions such as F- cannot approach the nitrogen atom on the oligoion. In contrast, weakly hydrated V ions accumulate close to the oligoion. These findings are consistent with the thermodynamic data and ongoing measurements of the dielectric relaxation in ionene solutions. (C) 2007 Elsevier B.V. All rights reserved.