Small angle neutron scattering in combination with dynamic and static light scattering has been used to evaluate the association behavior of the styryl- and dienyllithium head groups in benzene. Both types of lipophobic active centers were found to-aggregate as dimers which in turn can self-assemble to yield large scale structures. For the dienyllithium systems no evidence for the presence of tetrameric aggregates was found. The assay of the large scale structures revealed them to be prolate ellipsoids. Thus, these model ionomer systems exhibit diblock copolymer and surfactant style behavior in their capacity to generate cylindrical micelles.