O-Antigens and core oligosaccharides from bacterial lipopolysaccharides (LPS) are often structurally unique and immunologically active, have become attractive targets in the development of antibacterial vaccines. Structurally well-defined and pure oligosaccharides can be used in identifying protective epitopes of the carbohydrate antigens, which is important for the design of an effective vaccine. Here, the recent progress on chemical synthesis and immunological evaluation of glycans related to O-antigens and core oligosaccharides from bacterial LPS are summarized.