With chitosan of various characteristics and hyaluronic acid mixtures in aqueous solutions, we prepare polyelectrolyte complexes (PECs) which have many potential biomedical applications. We use a processing route, desalting, which consists in starting from homogeneous solutions at high salt concentration and the salt is slowly extracted from the polysaccharides solution by dialysis, which modifies the ionic content of the solution. Our results have shown that the chitosan/hyaluronic acid PECs that we process can take the form of a macrogel. Its mechanical properties are strongly dependant on the preparation history. The purpose of the proposed Neutron Scattering experiments is to characterize and identify the key structural aspects which lead to the formation macrogels showing various mechanical behaviors particularly by comparing the structure of macrogels obtained from similar solutions but with changing processing routes. Furthermore scattering performed with in situ deformed macrogels under various strains is considered to better understand the effect of each polysaccharide constituting the macrogels.