The new method for preparing hybrid fibers from aqueous solution is described. The method is based on interfacial polyionic complexation between the counter-charged polymers. Polysaccharides, chitosan and gellan, and polypeptides, poly(L-lysine) and poly(L-glutamic acid) were utilized as the components of the fibers. The chitosan-gellan and poly(L-lysine)-gellan hybrid fibers exhibited a high level biodegradability.