This paper presents the results of a study of the chemical structure and morphology of polyblends of chemically modified chitin and chitosane with poly(ethylene oxide). Poly(ethylene oxide)(PEO) forms a compatible one-phase blend with chitosane acetate salt (PEO/CHIACA) and a non-compatible two phase blend with dibutyrylchitin (PEO/DBCHI). The compatible one-phase blend of PEO/CHIACA is formed due to the formation of strong hydrogen bonds between ether groups in PEO and hydroxy groups in CHIACA. Chemical and crystalline morphological structure is discussed here.