The interaction of macromolecules of the components of polymer complexes (PCs) based on poly-N-vinylpyrrolidone or polyethylene glycol with chitosan succinyl is studied by spectral and rheological methods. The presence of cooperative interaction between molecules through hydrogen bonds in the studied systems is proved by the spectroscopic method. It is shown that varying the molar ratio of polymers in the complexes changes the degree of the structuring of solutions based on them, which, in turn, affects the gel-forming and film-forming properties of the resulting systems. It is found that film materials based on individual polymers are characterized by low values of the contact angle of wetting. This indicates the high level of hydrophilicity of these materials, while films based on PCs have a lower surface hydrophilicity. Therefore, by modifying poly-(N-vinylpyrrolidone) or polyethylene glycol with chitosan succinyl, it is possible to impart greater lyophilicity to materials based on them, which will contribute to the multipoint interaction with them of active centers of biomacromolecules of the body.