Physico-chemical pretreatment of lignocellulosic biomass is critical in removing substrate-specific barriers to cellulolytic enzyme attack. Alkaline pretreatment successfully delignifies biomass by disrupting the ester bonds cross-linking lignin and xylan, resulting in cellulose and hemicellulose enriched fractions. Here we report the use of dilute alkaline (NaOH) pretreatment followed by enzyme saccharifications of wheat straw to produce fermentable sugars. Specifically, we have assessed the impacts of varying pretreatment parameters (temperature, time and alkalinity) on enzymatic digestion of residual solid materials. Following pretreatment, recoverable solids and lignin contents were found to be inversely proportional to the severity of the pretreatment process. Elevating temperature and alkaline strengths maximised hemicellulose and lignin solubilisation and enhanced enzymatic saccharifications. Pretreating wheat straw with 2% NaOH for 30 min at 121 °C improved enzyme saccharification 6.3-fold when compared to control samples. Similarly, a 4.9-fold increase in total sugar yields from samples treated with 2% NaOH at 60 °C for 90min, confirmed the importance of alkali inclusion. A combination of three commercial enzyme preparations (cellulase, β-glucosidase and xylanase) was found to maximise monomeric sugar release, particularly for substrates with higher xylan contents. In essence, the combined enzyme activities increased total sugar release 1.65-fold and effectively reduced cellulase enzyme loadings 3-fold. Prehydrolysate liquors contained 4-fold more total phenolics compared to enzyme saccharification mixtures. Harsher pretreatment conditions provide saccharified hydrolysates with reduced phenolic content and greater fermentation potential.