Hemicelluloses are widely used to prepare gel materials because of their renewability, biodegradability, and biocompatibility. Here, molecular chain extension of hemicelluloses was obtained in a two-step process. Composite hydrogels were prepared via free radical graft copolymerization of crosslinked quaternized hemicelluloses (CQH) and acrylic acid (AA) in the presence of crosslinking agent N,N'-methylenebisacrylamide (MBA). This chain extension strategy significantly improved the mechanical performance of the resulting hydrogels. The crosslinking density, compression modulus, and swelling capacities of hydrogels were tuned by changing the AA/CQH and MBA/CQH contents. Moreover, the biocompatibility test suggests that the hemicelluloses-based hydrogels exhibited no toxicity to cells and allowed cell growth. Taken together, these properties demonstrated that the composite hydrogels have potential applications in the fields of water absorbents, cell culture, and other functional biomaterials.