In this study, an RG-I pectin DNP-W6 was isolated from the stems of Dendrobium nobile Lindl. (Orchidaceae). It contained mannose, glucose, galactose, galacturonic acid and rhamnose in a molar ratio of 0.6: 1.0: 1.5: 1.1: 1.0. Its structural features were revealed by chemical, physical and spectral analysis. The results suggested that DNP-W6 possessed a backbone of a disaccharide of !4)-a-GalAp-(1!2)-a-Rhap-(1!, with approximate 50% substitution at O-4 of the rhamnopyranosyl residues. The side chains were neutral chains including galactosyl, mannosyl and glucosyl chains. The acetyl content was estimated to be 8.9%. The immunological results indicated that DNP-W6 and its derivatives exhibited different immunological activities in vitro, showing that the side chains and acetyl groups had an important effect on the expression of immunological activities.