Lignocellulosic biomass is available in large quantities and constitutes an attractive feedstock for the sustainable production of bulk and fine chemicals. Although methods have been established for the conversion of its cellulosic fractions, valorization of lignin has proven to be challenging. The difficulty in disassembling lignin originates from its heterogeneous structure and its propensity to undergo skeletal rearrangements and condensation reactions during biorefinery fractionation or biomass pretreatment processes. A strategy for hindering the generation of these resistive interunit linkages during biomass pretreatment has now been devised using formaldehyde as a stabilizing agent. The developed method when combined with Ru/C-catalyzed hydrogenolysis allows for efficient disassembly of all three biomass fractions: (cellulose, hemicellulose, and lignin) and suggests that lignin upgrading can be integrated into prevailing biorefinery schemes.