A hydrophilic interaction liquid chromatography( HILIC)-mass spectrometric( MS) method was developed for the analysis of glycosaminoglycan( GAG) oligosaccharides. By using 5 mmol / L NH4 Ac as the mobile phase which was compatible with MS,four types of HILIC columns were investigated to analyze GAG oligosaccharides. The results showed that,amino-HILIC column was unsuitable for all glycosaminoglycan( GAG) oligosaccharides,amide-HILIC column was useful only for hyaluronan oligosaccharides from dp2 to dp20,zwitterionic phase HILIC column was useful for hyaluronan oligosaccharides from dp2 to dp30 and to a lesser extent for chondroitin oligosaccharides from dp2 to dp12,and diol-HILIC column afforded excellent resolution of hyaluronan( dp2- dp30), chondroitin sulfate( dp2- dp20) and heparin( dp4- dp20)oligosaccharides. In conclusion,different HILIC columns were investigated and on the basis of this,GAG oligosaccharides were separated and then analyzed by HILIC- MS method. The developed methods have higher resolution and better compatibility of MS.