The ability to manipulate block copolymers on the nanoscale has led to many scientific and technological advances. These include nanoscale ordered bulk and thin films and also solution phase components; these are promising materials for making smaller ordered electronics, selective membranes, and also biomedical applications. The ability to manipulate block copolymer material architectures on such small scales has risen from thorough investigations into the properties that affect the architectures. Polyelectrolytes are an important class of polymers that are used to make amphiphilic block copolymers. In this context the authors synthesized polystyrene-b-polyphosphonium block copolymers with different anions coordinated to the polyphosphonium block in order to study the effect of the anion on the aqueous self-assembly of the polymers. The anions play an important role in the solubility of the monomeric materials which results in differences in the self-assembly observed through dynamic light scattering and transmission electron microscopy.