A capillary electrophoresis with laser induced fluorescence detection(CE-LIF) method was developed for the determinations of polysaccharides in traditional Chinese medicines(TCMs) and N-glycome in human serum glycoprotein in this paper.After pre column derivatized with 9-aminopyrene-1,4,6-trisulfonate(APTS) by reductive amination,the seven monosaccharides were sufficiently separated within 15 min.In the analysis of real samples,the average recoveries for the analytes were all in the range of 88.0%-102% with relative standard deviations(RSDs) lower than 3.0%.The method is sensitive,accurate and reliable,and is suitable for the determination of monosaccharide composition in Chinese medicinal preparation.Meanwhile,fingerprints of N-glycome in human serum were established based on capillary gel electrophoresis(CGE).A poly(vinly alcohol) neutrally coated column was used to suppress the electroosmotic flow which would increase the analysis time,and the excellent separation of glycan isomers was realized.5 μL human sera was analyzed and a total of 17 fractions were isolated(RFU>0.2).The analysis of N-glycan profile has made it possible to research the glycosylation alterations of complex biological fluid.