Starchy content [wt%] Amylose Amylopectin To elaborate on our results and to assess the origin of the GVL, pure cellulose and hemicellulose were investigated as model substrates using the combination of Ru-MACHO-BH/H3PO4(aq)/H2. A total of 49% yield of GVL is obtained from 0.6 M of cellulose using 0.5 mol% Ru-MACHO-BH and 9.3 M H3PO4(aq) under 30 bar H2 pressure at 140 °C after 96 hours. In general, hemicellulose requires significantly milder conditions than cellulose. Two different types of xylans from different biomass sources were employed as feedstock, i.e. from beechwood and corn core. With 0.6 M beechwood xylan, 13% of GVL was obtained when using 0.5 mol% loading of Ru-MACHO-BH and 5.7 M H3PO4(aq) at 140 °C and 30 bar H2 in H2O for 48 hours. Interestingly, changing the solvent to a 1:1 V/V EtOH/H2O mixture afforded 43% GVL from beechwood xylan and 33% from corn core xylan. These results indicate that the catalytic system has excellent performance towards integrating the cascade of distinct acid-and hydrogenationmediated steps of both cellulose and hemicellulose. Finally, to investigate the fate of the catalyst, a test reaction was performed using Ru-MACHO-BH and sawdust under typical reaction conditions followed by NMR analysis. The persisting ligand phosphine shifts at approximately 63 ppm in P NMR suggests that the catalytic complex stays intact (SI, Figure ). The absence of a hydrido peak, including the disappearance of the hydrido triplet in 1 H NMR at -12.3 ppm of Ru-MACHO-BH, might suggest that the resting species is a di-phosphato Ru-complex in presence of excess phosphoric acid and absence of a H2 pressure (SI, Figure ). Alternatively, the hydrido(s) might be interacting with the weak acid, thereby obscuring the NMR signal .