Determination of monosaccharides in polysaccharides is reported by gas chromatography with OV-225 capillary column. Monosaccharides from the polysaccharides hydrolyzed in aqueous trifluoroacetic acid are reduced by NaBH4. Reduced monosaccharides are derivatized into sugar alcohol acetates with acetic anhydride pyridine before determination. The method was used to determine monosaccharides in polysaccharides from flak, angelica sinensis, and laminaria. The results showed that the monosaccharides in polysaccharide included rhamnose, arabinose, xylose, galactose and glucose for flax; rhamnose, arabinose, galactose and glucose for angelica sinensis; fucose, galactose, mannose, glucose and xylose for laminaria.