A catalytic process for the upgrading of woody biomass into mono-aromatics, hemi-cellulose sugars and a solid cellulose-rich carbohydrate residue is presented. Lignin fragments are extracted from the lignocellulosic matrix by cleavage of ester and ether linkages between lignin and carbohydrates by the catalytic action of homogeneous Lewis acid metal triflates in methanol. The released lignin fragments are converted into lignin monomers by the combined catalytic action of Pd/C and metal triflates in hydrogen. The mechanism of ether bond cleavage is investigated by lignin dimer models (benzyl phenyl ether, guaiacylglycerol-β-guaiacyl ether, 2-phenylethyl phenyl ether and 2-phenoxy-1-phenylethanol). Metal triflates are involved in cleaving not only ester and ether linkages between lignin and the carbohydrates but also β-O-4 ether linkages within the aromatic lignin structure. Metal triflates are more active for β-O-4 ether bond cleavage than Pd/C. On the other hand, Pd/C is required for cleaving α-O-4, 4-O-5 and β-β linkages. Insight into the synergy between Pd/C and metal triflates allowed optimizing the reductive fractionation process. Under optimized conditions, 55 wt% mono-aromatics - mainly alkylmethoxyphenols - can be obtained from the lignin fraction (23.8 wt%) of birch wood in a reaction system comprising birch wood, methanol and small amounts of Pd/C and Al(III)-triflate as catalysts. The promise of scale-up of this process is demonstrated.