Polyelectrolyte-surfactant complexes made of poly(styrenesulfonate) and various cationic surfactants are "synthesized" by common precipitation in water. Redissolved in polar organic solvents, these complexes show polyelectrolyte behavior. This behavior is quantitatively described with a modified Hess-Klein equation where the fitting parameters have the meaning of a hydrodynamic size, an effective charge density, and a salt concentration. The influence of complex hydrophobicity, the polarity of the solvent, and the role of small amounts of water are discussed by means of the experimentally determined Hess-Klein parameters. Dynamic light scattering in dilute solutions reveals a complex relaxation typical for coupled or strongly interacting systems.