The present work, in which cellulose isolated from formic acid fractionation (FAC) is decorated with polyetherimide (PEI) to attain highly efficient cellulose-derived PdAgbimetallic catalyst (PdAg-PEI-FAC), has been investigated, and the catalyst properties are characterized by XRD, XPS, BET, ICP-AES and HAADF-STEM. The as-obtained Pd3.75Ag3.75-PEI-FAC exhibits excellent catalytic performance for H2 evo-lution from a sodium formate-free formic acid (FA) aqueous medium at ambient temperature and the turnover frequency (TOF) reaches a high value of 2875 h-1, which is superior to most of the previously reported Pd-based heterogeneous catalysts supported on a carbon matrix in the literature. The remarkable catalytic activities of PdAg-PEI-FAC result from high dispersion Pd and synergistic effects between the PdAg bimetallic system. Furthermore, the amide (-NH) group in PEI coated on cellulose acting as a proton scavenger efficiently improves the catalytic property of catalyst. In addition, the critical factors affecting H2 release, such as FA concentration, reaction temperature, PdAg compositions and support matrix type, are also evaluated. Based on the experimental results, the probable three-step mechanism of H2 evolution from FA over Pd3.75Ag3.75-PEI-FAC is proposed. In the end, the activation energy (Ea) of Pd3.75Ag3.75-PEI-FAC catalyst is calculated to 53.97 kJ mol-1, and this catalyst shows unique robustness and satisfactory re-usability with no loss of catalytic activity after five recycles. The findings in this work provide a novel routine from lignocellulose fractionation towards cellulose-derived catalyst for H2 evolution.