Objective: To separate polysaccharides from Radix Codonopsis and identify the monosaccharides and their molar ratio.Methods: The molecular weights were tested by High performance gel permeation chromatography.The components of the polysaccharides were identified by gas chromatography-mass spectrometry(GC-MS).Monosaccharides from polysaccharides were derivatized to acetylated aldononitriles before determination.Results: Polysaccharide were composed of CPS'-3 and CPS'-4,all including rhamnose,arabinose and galactose,with the molar ratio of 1.5∶2.7∶4.6,1.3∶0.9∶2.6 in different CPS.They were newly discovered polysaccharides in Radix Codonopsis.Conclusion: CPS were made up of rhamnose,arabinose and galactose.The GC-MS was eligibled for the analysis of Radix Codonopsis polysaccharides.