Mild alkali cooking of lignocellulosic biomass is an effective pretreatment method, which improves enzymatic hydrolysis. Here, we report the use of dilute alkali (NaOH) pretreatment followed by enzyme saccharification of cereal residues for their potential to serve as feedstock in the production of next-generation biofuels in Australia. After pretreatment, both solids and lignin content were found to be inversely proportional to treatment severity. We also found that higher temperatures and alkali strength were quintessential for maximizing sugar recoveries from enzyme saccharifications. Generally, pretreatment conditions at elevated temperatures led to highly digestible material enriched in both cellulose and hemicellulose components. Increasing cellulase loadings and tailoring enzyme activities with additional β-glucosidases and xylanases delivered greater rates of monosaccharide sugar release and yields throughout enzyme hydrolysis. Considering their abundance, high sugar potential, and apparent ease of conversion, cereal crop residues are an excellent feedstock for the production of second-generation fuels and/or biorefineries.