α-1,6-Graft-α-1,3-glucan comprises a main-chain of α-1,6-glucan and side-chains of α-1,3-glucan. It was synthesized by a one-pot in vitro enzymatic polymerization of sucrose and dextran (α-1,6-glucan) of different molecular weights. In the presence of the high-molecular-weightdextran (Mw ≥ 650 000), the graft glucan formed a self-standing hydrogel without any cross-linker. It was possible to control the number of α-1,3-glucan side-chains by controlling the molecular weight and concentration of the dextran. Consequently, it was possible to control the compression strength of the obtained gels. Hydrogels of the graft glucan were formed by physically cross-linking the α-1,3-glucan side-chains. These physical gels are potentially useful biomaterials with high biocompatible, because the graft glucan is composed of glucose alone.