Composite materials based on natural polysaccharides and polyguanidines are considered. The synthesis mechanisms and structural features of composite materials based on polyguanidines and polysaccharides are discussed. The issues of the relationship of their structure with antimicrobial activity are highlighted. It has been shown that the modification of polysaccharides with guanidine-containing compounds makes it possible to give them bactericidal properties, increase strength and solubility, and is a promising direction for the development of new-generation drugs.