Polyelectrolyte complexes have a wide range of applications for surface modification and flocculation and sorption of organic molecules from solutions. As an example, complexes between poly(diallyl dimethyl ammonium chloride) and poly(styrene sulfonate) have been investigated by diffusion and electrophoresis NMR. The formation of primary or soluble complexes is monitored. The hydrodynamic size is characterized by the hydrodynamic radius, calculated from the diffusion coefficient determined by pulsed field gradient NMR. In the combination with electrophoresis NMR, the effective charge of the molecules and complexes is determined. The hydrodynamic size of the primary complex is smaller than that of the pure polyelectrolyte of the larger molecular weight, in the present case poly(styrene sulfonate), in solution, since charges are compensated by the oppositely charged polyelectrolyte and hence the repelling forces diminish. The effective charge of the complexes is drastically reduced.