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Lignocellulosic bioethanol is currently being explored as a substitution to fossil fuels. Many lignocellulosic materials are being examined but the importance is to find those with attractive agro-energy features. Producing lignocellulosic ethanol is challenging because lignocellulosic biomass is resistant to chemical and biological degradation. To reduce biomass recalcitrance, a pretreatment stage is required. Pretreatment is considered to be the most intensive operating/operating cost component of cellulosic ethanol production. Therefore, research is heavily focused on understanding the effect of pretreatment technologies on the fundamental characteristics of lignocellulosic biomass. The first study in the thesis investigates Buddleja davidii as a potential biomass source for bioethanol production. The work focuses on the determination of ash, extractives, lignin, hemicellulose, and cellulose content in this plant, as well as detailed elucidation of the chemical structures of both lignin and cellulose by NMR spectroscopy. The study showed that B. davidii has several unique agro-energy features as well as some undesired characteristics. The second study presents research on the ethanol organosolv pretreatment (EOP) of B. davidii and its ability to produce enzymatically hydrolysable substrates. It was concluded that the removal of hemicellulose, delignification, reduction in the degree of polymerization (DP) of cellulose, and the conversion of crystalline cellulose dimorphs (Iα/Iβ) to the easily degradable para-crystalline and amorphous celluloses were the characteristics accounted for efficient enzymatic deconstruction of B. davidii after EOP. The third study provides a detailed elucidation of the chemical structure of ethanol organosolv lignin (EOL) of B. davidii by NMR spectroscopy. Such research was needed to understand the pretreatment mechanism in the context of delignification and alteration of the lignin structure. Future applications of the resulted EOL will be valuable for industrially viable bioethanol production process. EOP mainly cleaved β-O-4' interlinkages via homolysis, decreased the DP of lignin, and increased the degree of condensation of lignin. EOL had low oxygen content, molecular weight, and aliphatic OH as well as high phenolic OH, which are qualities that make it suitable for different co-product applications. The last study provides information on the anatomical characteristics of pretreated B. davidii biomass after EOP. The importance of this research was to further understand the alterations that occur to the cellular structure of the biomass which can then be correlated with its enzymatic digestibility. The results concluded that the physical distribution of lignin within the biomass matrix and the partial removal of middle lamella lignin were key factors influencing enzymatic hydrolysis.