The invention provides a method for determining the structure of a carbohydrate sample, comprising perbenzoylating a carbohydrate sample with a perbenzoylating agent to protect free hydroxyl groups in the carbohydrate sample; cleaving the glycosidic linkages of the perbenzoylated carbohydrate sample by contacting the carbohydrate sample with an amount of BrCH2COBr/H2O effective to cleave the carbohydrate sample; treating the resulting product with AgOAc and methanol or AgOTf/TMU and methanol to effect glycosidation; treating the resulting product with thiourea to remove bromoacetate groups; subjecting the resulting product to effect methoxycinnamoylation of free hydroxyl groups; separating the resulting benzoates with high-pressure liquid chromatography; performing mass, ultraviolet and circular dichroic spectroscopy on the separated benzoates; and comparing the spectra so obtained with reference spectra or calculated values to identify the structure of the carbohydrate. The invention also provides an apparatus for automatically determining the structure of a carbohydrate molecule such as an oligosaccharide.