Napier grass is a promising energy crop in the tropical region. Feasible alkaline pretreatment technologies, including NaOH, Ca(OH)(2), NH3, and alkaline H2O2 (aH(2)O(2)), were used to delignify lignocellulose with the aim of improving glucose recovery from Napier grass stem cellulose via enzymatic saccharification. The influences of the pretreatments on structural alterations were examined using SEM, FTIR, XRD, and TGA, and the relationships between these changes and the enzymatic digestibility of cellulose were addressed. The extensive removal of lignin (84%) in NaOH-pretreated fibre agreed well with the high glucan conversion rate (94%) by enzymatic hydrolysis, while the conversion rates for fibre pretreated with Ca (OH)(2), NH3, and aH(2)O(2) approached 60%, 51%, and 42%, respectively. The substantial solubilisation of lignin created porosity, allowing increased cellulose accessibility to cellulases in NaOH-pretreated fibre. In contrast, high lignin content, lignin redeposition on the surface, and residual internal lignin and hemicellulose impeded enzymatic performance in Ca(OH)(2)-, NH3-, and aH(2)O(2)-pretreated fibres, respectively. (C) 2016 Elsevier Ltd. All rights reserved.