The present study highlights the performance of carbocation scavengers for the pretreatment of hardwood biomass followed by the production of bio-based products. The behaviour of different carbocation scavengers namely; 2-Napthol, 4 Hydroxybenzoic acid, Vanillic acid, Catechol, Hydroquinone, Resorcinol and Phenol and their mitigating effect on the rate of hydrolysis was explored under different operating conditions. All the carbocation scavengers show significant changes in the crystallinity index leading to distinct morphological and physiochemical changes in the biomass structure. Results revealed that the addition of carbocation scavengers not only reduces the inhibitory effect of structured lignin but also enhances the accessibility of cellulose and hemicellulose and facilitates the production of sugars and 5-Hydroxymethyl Furfural. Maximum 5-HMF yield was observed using 2-Napthol at an optimised concentration of 2 wt% (1.5 mL) at 190 °C in 60 min. Further, to evaluate the effect of acetyl groups, biomass deacetylation was also performed. The highest deacetylation effect was observed at 170 °C and showed ∼73% and ∼94% reduction in the holocellulosic content in 60 min. The proposed study develops a sustainable and viable route to suppress the inhibitory effect of lignin with the utilization of carbocation scavengers and enhances biomass digestibility that favours the production of bio-based chemicals.