ABSTRACT Thermochemical pretreatment is an interesting approach for the effective separation of lignocellulosic biomass before fermentation for bioethanol production. This research focused on optimising the thermochemical pretreatment conditions of cassava waste using response surface methodology to predict the glucose yields under the optimal condition. The optimised conditions of 0.045 M of NaOH concentration at 153.59 °C for 48.03 min resulted in the maximum glucose yield of 93.87%. In addition, fermentation process can generate ethanol within a range of solid loading from 10% to 20%. The highest concentration of ethanol was 34.53 ± 0.56 g/L after 72 h, equivalent to ethanol yield of 0.46 g/g. The co-products were also characterised for further utilisation in biorefinery concept. The results of this study confirmed that the thermochemical pretreatment process using the NaOH catalyst could provide high glucose yields, which can be easily converted into bio-based fuels and further valorised of co-products to value-added chemicals.