Chemical synthesis of the hexasaccharide repeating unit associated with the exopolysaccharide of Lactobacillus mucosae VG1 is reported. The total synthesis is accomplished through a convergent [2 + 2 + 2] strategy using rationally protected monosaccharide derivatives. Chemoselective activation of the glycosyl donors and regioselective nucleophilicity of the acceptors were successfully employed throughout the chemical synthesis.