The limitation of the fossil-resources has led the research to focus on the production of biomass-based fuels from lignocellulosic agricultural residues, as it is the case of the bio-ethanol. Due to the complex and heterogeneous structure of these residues, a delignification stage is usually necessary prior to a simultaneous saccharification and fermentation treatment (SSF) for the production of bio-ethanol. In a previous work, an alkaline delignification of hydrothermally pretreated vine shoots using conventional heating was carried out in order to obtain a solid residue with low lignin and hemicellulosic content, which could be further subjected to a SSF treatment. However, when this biorefinery scheme was evaluated by a Life Cycle Assessment it was observed that the energy and chemical requirements of the delignification stage needed to be reduced. Therefore, in this work the assistance of the alkaline delignification stage by microwave was studied. The treatments were carried out at different temperatures, in order to study its influence on the lignin removal. It was observed that the microwave assistance could permit the improvement of the delignification treatments not only by increasing the delignification yield but also by reducing the temperature, time and NaOH concentration used in the treatments. The strong influence of the temperature on the chemical composition, structure and crystallinity of the delignified solids was also appreciated during this study. The solid residues obtained under the most severe conditions of the microwave-assisted alkaline delignification treatment (125 ºC) could be a promising solid for the employment in a SSF treatment due to its low lignin and hemicellulosic content (16.68 % and 0.01 % respectively) and its high glucan content (50.75 %), although it presented a higher crystallinity index than the hydrothermally pretreated vine shoots.