Sugar solutions are obtained from polysaccharide enriched biomass by contacting biomass with water and at least one nucleophilic base to produce a polysaccharide enriched biomass comprising a solid fraction and a liquid fraction. The solid fraction is separated from the lignin-containing liquid fraction and contacted with an acid solution, the acid solution comprising about 70 weight percent to about 100 weight percent sulfuric acid or an acid mixture comprising phosphoric acid and sulfuric acid, at a temperature and for a reaction time sufficient to produce a decrystallized biomass mixture. Water is added and the diluted biomass mixture is then hydrolyzed to produce a saccharification product comprising sugars.