Si has the highest theoretical capacity (4200 mA h g−1 ) among conventional anode materials, such as graphite (372 mA h g−1 ), but its large volume expansion leads to deterioration of the battery performance. To overcome this problem (issue), we investigated the use of polysaccharide-based 3D cross-linked network binders for Si anodes, in which the polysaccharide formed an effective 3D cross-linked network around Si particles via cross-linking of polysaccharide with citric acid (CA). Sodium alginate (SA), a natural polysaccharide extracted from brown algae, is a suitable binder material for Si anodes because its abundant hydroxyl (−OH) and carboxyl (−COOH) groups form hydrogen and covalent bonds with the −OH groups present on the Si surface. We found that CA-cross-linked (CA-SA) could effectively prevent the volume expansion of Si anodes through the formation of 3D cross-linked network structures. In addition, the CA-SA binders provide enhanced adhesion strength, enabling the fabrication of more robust electrodes than those prepared using binders with linear structures (“linear binders”). In particular, the fabricated Si-based electrode (high mass loading of 1.5 mg cm−2 ) with CA-SA binder exhibited outstanding areal capacity (∼2.7 mA h cm−2 ) and excellent cycle retention (∼100% after 100 cycles).