Hemicellulose materials are arguably the second most abundant renewable component of lignocellulosic biomass after cellulose. They are relatively under-utilized hetero-polysaccharides present in lignocellulosic biomass. In this research an alkaline treatment was optimized for extraction of polymeric hemicellulose from fully bleached hardwood pulp (B-HWP) and partially delignified switchgrass (SWG). The hemicellulose extracted from B-HWP was relatively pure with zero percent lignin and 89.5% xylose content whereas the partially delignified SWG hemicellulose contained about 6-3% lignin and 72–82% xylose, depending on the NaOH concentration during extraction (3–17% NaOH solution). A maximum molecular weight of SWG hemicellulose of 64,300 g/mol was achieved for the 10% NaOH solution extraction, whereas the MW of B-HWP hemicellulose at 10% NaOH solution extraction was lower at 49,200 g/mol. We have demonstrated that the residual lignin in SWG hemicellulose lowered the system Tg and this might be utilized as a way to increase the applications of hemicellulose in high value biomaterials. Furthermore, the hemicellulose could be crosslinked with zirconium to develop a water resistant gel for coating or adhesive applications. Our results showed that the loading stress required to break an hemicellulose based adhesive connection between two paper surfaces was 0.89, 2.02, 2.75, 3.46, and 3.11 (MPa) for 2, 4, 6, 8 and 10% AZC samples, indicating that up to about 8% AZC crosslinker in the hemicellulose increases the adhesive behavior of the material.