•(FA)–Pd/HPC–NH2 achieves the selective HDO of benzyl ketones from mixed oxygenates•H+/H? species accelerates hydrogenation C=O bond in ketones•Formate intermediates expedite cleavage Cbenzyl–O via an EDDO pathway•Proposing a green route to produce biofuels or chemicals only biomass Producing value-added and renewable rather than fossil fuels is reckoned as effective recipe against global warmi...