Polyelectrolyte complexes (PEC) were formed between a cationic polyamideamine epichlorohydrine condensate (PAE) and an anionic carboxymethylcellulose (CMC) at different ratios between the polymers, orders of mixing, salt concentrations and polymer concentrations. Firstly the polymers were characterised by polyelectrolyte titration (charge), static light scattering (molecular weight, radius of gyration) and measurements with a scanning interferometric refractometer (refractive index). The complexes were characterised by ocular inspection and static light scattering in combination with a special evaluation algorithm allowing an estimation of the geometric form of the complexes. The results show that the initial complexes have a spherical form and that the size is fairly constant over a large range of charge ratios between the polymers, provided the complexes are formed in deionised water. When the charge mixing ratio exceeded neutrality a secondary agglomeration of the initially formed complexes occurred. The presence of salt during PEC formation caused a dependence of the level of aggregation on the mixing ratio, whereby small amounts of NaCl drastically lowered the particle mass at lower mixing ratios. Subsequent addition of salt to PECs formed in water led to a strong swelling of the complex particles and at a critical salt concentration to dissolution.