Hemicellulose is the second most abundant biomass </span><span style="font-family:Verdana;">in </span><span style="font-family:Verdana;">the world. Because of its unique chemical structure, hemicellulose has attracted more and more research and industry application under the background of fossil resource shortage and drawbacks. Hem</span><span style="font-family:Verdana;">i</span><span style="font-family:Verdana;">cellulose is ten</span><span style="font-family:Verdana;">ded</span><span style="font-family:Verdana;"> to be modified with esterification, etherification, cross-linkage and so on. These reactions change hemicellulose properties, so that it could be applied in many fields such as medical field, films, hydrogels, conductive polymers. Herein, we reviewed structure, isolation, reaction and applications of hemicellulose. Especially the useful pathways to change the hydrophilic character of hemicelluloses to hydrophobic are reviewed and several applications of these materials are discussed.