The ‘lignin-first’ approach has recently gained attention as an alternative whole biomass pretreatment technology with improved yield and selectivity of aromatics compared with traditional upgrading processes using technical lignins. Metal triflates are effective co-catalysts that considerably speed up the removal of lignin fragments from the whole biomass. As their cost is too high in a scaled-up process, we explored here the use of HCl, H2SO4, H3PO4 and CH3COOH as alternative acid co-catalysts for the tandem reductive fractionation process. HCl and H2SO4 were found to show superior catalytic performance over H3PO4 and CH3COOH in model compound studies that simulate lignin-carbohydrate linkages (phenyl glycoside, glyceryl trioleate) and lignin intralinkages (guaiacylglycerol-β-guaiacyl ether). HCl is a promising alternative to the metal triflate as co-catalyst in the reductive fraction of woody biomass. Al(OTf)3 and HCl respectively afforded 46 wt% and 44 wt% lignin monomers from oak wood sawdust in a tandem catalytic systems with Pd/C at 180 ⁰C in 2 h. The retention of cellulose in the solid residue was nearly similar.