A simple capillary electrophoretic method based on 1-phenyl-3-methyl-5-pyrazolon (PMP) derivatization has been developed for simultaneous separation and determination of nine aldoses (xylose, arabinose, glucose, rhamnose, fucose, galactose, mannose, glucuronic acid and galacturonic acid). The separation of PMP-labeled monosaccharide derivatives was carried out in uncoated capillary (48.5 cm×75 μm i.d.) and under the selected optimum conditions of pH 11.0, 200 mM borate buffer at applied voltage 15 kV and capillary temperature 20 °C, the nine PMP-monosaccharides could be perfectly separated from each other within 40 min. Furthermore, the developed method was firstly applied to determine the sugar composition in the polysaccharide isolated from Chinese Codonopsis pilosula. The results showed that C. pilosula polysaccharide was a typically acidic heteropolysaccharide and was composed of arabinose, glucose, rhamnose, galactose, mannose, glucuronic acid and galacturonic acid in the molar contents of 48.1, 103.5, 16.1, 48.5, 7.5, 4.2 and 119.1 μM, respectively. The assay results were satisfactory.