Chemical components of lignocellulosic biomass may impede biofuel processing efficiency. To understand whether the heartwood of Acacia confusa is suitable for biofuel application, extractive-free heartwood of A. confusa was subjected to dilute acid (DA) or sulfite pretreatments. Sugar recoveries were used to evaluate the performance of different pretreatments. Cell wall properties, such as 4-O-alkylated lignin structures, S/G ratios, and xylan contents, of the pretreated samples showed significant correlations with the enzymatic saccharification of glucan. 4% bisulfite pretreated samples produced higher total sugar recoveries than DA treated ones. The highest total sugar recoveries from DA and sulfite pretreatment were 52.0% (170 °C, 20 min) and 65.3% (4% NaHSO3 and 1% H2SO4), respectively. The results also demonstrated that the existence of extractives in the heartwood of A. confusa hindered the sugars recoveries from both the pretreatments and the enzymatic saccharification. Total sugar recoveries were reduced 11.7-17.7% in heartwood samples with extractives.