Milk oligosaccharides, which are free oligosaccharides in the mammalian milk, is one of the main composition in milk. Recent studies suggested that milk oligosaccharides improved immune function, and showed prebiotics as well as anti-infection actives. Milk oligosaccharides is also important for the intestinal development, neural development of infants. Buffalo (Bubalus bubalis) milk is the second important milk source besides cow milk. It was also well accepted that buffalo milk was rich in nutritional content and was a high quality dairy product with good taste. However, researches on buffalo milk oligosaccharides was limited and only worked on American buffalo. On the other hand, milk oligosaccharides on Chinese buffalo is lacking. In the present study, colostrum milk samples from Guangxi buffalo were purified with solid phase extraction and modified by Aniline (Bn) derivative reagent. The sample was further purified by UPLC-ESI-Q-TOF-MS. The oligosaccharide components in buffalo colostrum were determined and compared with the cow colostrum milk. 19 kinds of oligosaccharides were found in cow colostrum and 9 in buffalo colostrum. Moreover, in both two kinds of colostrum, neutral disaccharide m/z 385.15, neutral trisaccharide m/z 547.21 and acidic oligosaccharide m/z 635.23 were the main composition. In general, the proportion of neutral oligosaccharides in buffalo milk was higher than that in cow milk, with a ratio of 88.88% and 63.16%, respectively.