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Cordyceps gunnii (berk.) Berk (C. Gunnii) is well known as a Chinese rare caterpillar fungus and has similar pharmacological activity with C. sinensis. In this work, a high-molecular-weight polysaccharide (CPS) was isolated and purified from the mycelia of C. gunnii. The total sugar content of CPS was amounted to 92.84%. The result of HPLC indicated that CPS was a homogeneous polysaccharide. The estimated average molecular weight of CPS was 3.72 ×106 Da. The specific rotation of CPS was recorded [˛]25 D = +134.2◦. Its characteristic was determined by chemical analysis, gas chromatography, IR spectroscopy and NMR data. The results showed that CPS was mainly composed of glucose,. | Carbohydrate Polymers 88 2012 1072-1076 Contents lists available at SciVerse ScienceDirect Carbohydrate Polymers journal homepage www.elsevier.com locate carbpol Structure and anti-tumor activity of a high-molecular-weight polysaccharide from cultured mycelium of Cordyceps gunnii Zhen-yuan Zhua Nian Liua Chuan-ling Sib Yang Liua Li-na Dinga Chen Jinga An-jun Liua Yong-min Zhangc a Key Laboratory of Food Nutrition and Safety Ministry of Education College of Food Science and Biotechnology Tianjin University of Science and Technology Tianjin 300457 PR China b Tianjin Key Laboratory of Pulp and Paper College of Materials Science and Chemical Engineering Tianjin University of Science and Technology Tianjin 300457 PR China c Université Pierre et Marie Curie-Paris 6 Institut Parisien de Chimie Moléculaire UMR CNRS 7201 4 Place Jussieu 75005 Paris France ARTICLE INFO ABSTRACT Article history Received 12 December 2011 Received in revised form 15 January 2012 Accepted 20 January 2012 Available online 28 January 2012 Keywords Cordyceps gunnii High-molecular-weight polysaccharide Characteristic Antitumor Cordycepsgunnii berk. Berk C. Gunnii is well known as a Chinese rare caterpillar fungus and has similar pharmacological activity with C. sinensis. In this work a high-molecular-weight polysaccharide CPS was isolated and purified from the mycelia of C. gunnii. The total sugar content of CPS was amounted to 92.84 . The result of HPLC indicated that CPS was a homogeneous polysaccharide. The estimated average molecular weight of CPS was 3.72 X 106 Da. The specific rotation of CPS was recorded a D5 134.2 . Its characteristic was determined by chemical analysis gas chromatography IR spectroscopy and NMR data. The results showed that CPS was mainly composed of glucose and a small amount of rhamnose arabinose xylose mannose and galactose with a molar ratio of Rha Ara Xyl Man Glu Gal 3.0 2.6 1.0 1.3 106.0 2.8. The main chain of CPS was majorly composed of a- 1 4 glucose. The tumor .