The overall kinetics of crystallization and melting behaviour of solid, semicrystalline blends PEO/chitosan in the form of thin films for a set of PEO species of various molecular weights and different blend compositions were correlated with a morphological structure of the blends. The negative values of the Flory-Huggins interaction parameter due to specific interactions by hydrogen bonding were evaluated. Avrami equation was applied to describe kinetics of crystallization of pure PEO and PEO/chitosan blends of various compositions.