We have studied the nano- and microparticles formed by complexation of PDAC [poly(diallyldimethylammoniumchloride)] and SDS (sodium dodecyl sulfate). The complexation phenomenon was characterized by light scattering and ζ-potential measurements. The nature of the complexes was revealed by direct-imaging cryogenic temperature transmission electron microscopy (cryo-TEM), showing nanometric details of the complexes formed around the point of neutralization. The images also reveal how those aggregates are solubilized by excess surfactant, first into faceted particles with threadlike micelles attached to their surfaces, prior to complete solubilization, then into lacelike aggregates, and finally into spheroidal micelles. The nanostructure of the complexes strongly suggests they are made of a hexagonal liquid crystalline phase. This was further supported by small-angle X-ray scattering (SAXS).