Secondary generation biofuels such as cellulosic biofuels rely on large portions of cellulosic bioresources, which may include forests, perennial grasses, wood and agricultural residues. Switchgrass is one promising feedstock for biofuel production. In the present study, thesis work focused on the chemical and structural profiles and hydrothermal pretreatment of switchgrass. Four populations of switchgrass were investigated for their chemical properties among populations and morphological portions, including the compositions of lignin and carbohydrates, extractives content, higher heating value (HHV), and syringyl:guaiacyl (S:G) ratio. The results demonstrate similar chemical profiles and lignin structure among the four populations of switchgrass. Morphological fractions of switchgrass including leaves, internodes, and nodes differ significantly in chemical profiles and S:G ratios of lignin. The structure of isolated cellulose from switchgrass SW9 is similar between leaves and internodes. The structure of isolated lignin from leaves and internodes of switchgrass SW9 differs in S:G ratio and molecular weight. Hydrothermal pretreatment of leaves and internodes indicates that a similar chemical composition and chemical structure for pretreated leaves and internodes. The degree of polymerization (DP) for cellulose of the pretreated internodes is 23.4% greater than that of the pretreated leaves. The accessibility of pretreated leaves measured by Simons' Staining technique is greater than that of pretreated internodes. Pretreated leaves have a 32.5-33.8% greater cellulose-to-glucose conversion yield than do pretreated internodes.