A fractionation process for producing value-added products from a lignocellulosic biomass, comprises: a) mechanically refining the lignocellulosic biomass under mild refining conditions to form a refined biomass pulp with enhanced susceptibility to separation of hemicellulose, cellulose and lignin, and enhanced digestibility of carbohydrates in hydrolysis b) separating hemicellulose and sulfur-free high-quality lignin from cellulose in the refined biomass, and, optionally c) producing various bioproducts from the above said process.