Carbohydrates are important structural and functional moieties of glycoproteins and glycolipids. Many important biological processes, such as development, immunology, cancer metastasis, etc. are mediated by the carbohydrates moieties of glycoconjugates. Oligosaccharides from most biological sources are of considerable complexity and variety. Understanding the precise roles they play in biological processes often required their isolation, detailed structural analyses and usage in functional assays. Generally oligosaccharides lack chromophore groups, which increase the difficulty of oligosaccharides structure analysis. Now a complete analysis of a carbohydrate oligomer is one of the foremost and compelling challenges in structural biology. We reviewed 28 references on the methods for solation and structure determination for oligosaccharides.