Condensation, dark color and low extraction yield of lignin have hindered the full valorization of biomass during lignocellulosic fractionation. Herein, we introduce a novel biomass fractionation concept that addresses the issue of lignin's spatial confinement. Building upon this concept, we have devised an environmentally friendly and straightforward strategy. This approach involves a combination of selective carboxylation at the Cγ-OH position using citric acid and etherification at the Cα-OH position using butanol. The objective is to mitigate the spatial confinement of lignin and stabilize its active intermediates for lignin extraction. Consequently, up to 91.4 ± 0.2% lignin with a light color can be separated from the recalcitrant softwoods, as a UV blocker to improve the performance of sunscreen cream. The cellulosic residue can be enzymatically digested to glucose with a yield of 80%. The initiated biomass fractionation theory and strategy in this study provide a new concept for the isolation of lignin and full valorization of lignocellulose, promoting the development of a sustainable economy.