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[Display omitted] • Additives in pretreatment notably raised fermentable sugars and bioethanol yields. • Mechanisms of reducing lignin repolymerization by additives were investigated. • −OH groups of additives suppressed lignin repolymerization by forming a new reaction. • More hydrophilic groups of lignin reduced non-specific binding into enzymes. • Enlarged biomass porosity and lower surface coverage reduced surface lignin barrier. Pretreatment is the key factor for producing fermentable sugars and biofuels from lignocellulosic biomass. However, during pretreatment lignin repolymerization occurs which reduces the efficiency of carbohydrates hydrolysis. In the present study, three additives (2-naphthol-7-sulfonate, 2-naphthol, and mannitol) were evaluated for boosting the effectiveness of combined pretreatment (liquid hot water + green liquor) of pine-wood biomass. The results revealed that supplied additives into combined pretreatment changed the physicochemical structure of lignin, therefore, alleviating the inhibitory effect of lignin repolymerization and notably raised sugars yield (glucose, xylose) ranging from 85% to 93%. XPS and FTIR analyses confirmed that −OH groups of additives led to lower formation of phenolic hydroxyl (PhOH) and higher hydrophilic groups of lignin, accounting for reduced non-specific binding of lignin into cellulase enzymes. Furthermore, additives increased surface lignin coverage, biomass porosity, and fiber swelling by 1.96–2.59, 1.66–1.86, and 1.13–1.29 folds respectively, comparing to corresponding sample without additives caused more liquified and extractable lignin, which notably reduced the surface lignin barrier. Hence, both factors including non-specific binding effect and surface lignin barrier, contributed to reducing lignin repolymerization, thereby increased cellulose accessibility for high production of fermentable sugars and bioethanol in softwood biomass. [ABSTRACT FROM AUTHOR]