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This study explored the physicochemical properties and prebiotic activities of glucans and oligoglucans. Oligoglucans were obtained through the fermentation of <i>Leuconostoc mesenteroides</i> CICC6055 and the glucansucrase of strain CICC6055, while glucans were obtained only through fermentation. Thin-layer chromatography and high-performance liquid chromatography identified enzymatically synthesized oligoglucans with a higher yield. Differential scanning calorimetry and derivative thermogravimetry analyses revealed the heat resistance of the glucans and oligoglucans at 280–300 °C. Fourier transform-infrared spectroscopy and nuclear magnetic resonance analyses demonstrated that their main chains were linked with α-1,6-glycosidic bonds accompanied by glucose residue branching. In vitro fermentation experiments demonstrated that they not only improved the contents of short-chain fatty acids but also raised the abundance of predominant flora, such as <i>Bacteroides</i>, <i>Firmicutes</i>, <i>Verrucomicrobia</i>, and <i>Proteobacteria</i>. These results implicate glucansucrase as an efficacious tool for the enzyme synthesis of oligoglucans. Furthermore, both polysaccharides with different degrees of polymerization may be beneficial in maintaining a healthy human gut.