Castor plant is used commonly for oil extraction and biodiesel synthesis. However, the residues during pruning are not being used effectively. These residues have the potential to be used as feedstock to produce bioethanol and other by-products. The present work assessed the eco-friendly autohydrolysis pretreatment of castor plant pruning residues at different severity factors (R0), applying a range of temperatures from 100 °C to 200 °C. The hydrolysis of pretreated solids was carried out using a commercial cellulases complex at different solid and enzyme loadings. The enzymatic hydrolysate with a higher glucose concentration was further subjected to fermentation using Saccharomyces cerevisiae ATCC 4126. The results showed an efficient xylan hydrolysis (77.5%) and a preservation of glucan up to 83% in the solids pretreated at an R0 of 5.78. The enzymatic hydrolysis of the pretreated solids at an R0 of 5.78 showed a glucose release of 2.9-fold higher than non-pretreated material. In the hydrolysate fermentation, a maximum ethanol production of 50.5 g/L was achieved (equivalent to 6.4% v/v), corresponding to a conversion efficiency of 98% and a biomass-to-ethanol conversion yield of 93.0 g of ethanol per kilogram of feedstock.