Electrocatalytic　hydrogenation　(ECH)　is　a　burgeoning　strategy　for　the　sustainable　utilization　of　hydrogen.　However,　how　to　effectively　suppress　the　competitive　hydrogen　evolution　reaction　(HER)　is　a　big　challenge　to　ECH　catalysis.　In　this　study,　amine　(NH2-R)-coordinated　Pd　nanoparticles　loaded　on　carbon　felt　(Pd@CF)　as　a　catalyst　is　successfully　synthesized　by　a　one-step　solvothermal　reduction　method　using　oleylamine　as　the　reducing　agent.　An　exceptional　ECH　reactivity　on　benzaldehyde　is　achieved　on　the　optimal　Pd@CF　catalyst　in　terms　of　a　high　conversion　(89.7%)　and　selectivity　toward　benzyl　alcohol　(89.8%)　at　−0.4 V　in　60 min.　Notably,　the　Faradaic　efficiency　for　producing　benzyl　alcohol　is　up　to　90.2%,　much　higher　than　that　catalyzed　by　Pd@CF-without　N-group　(41.1%)　and　thecommercial　Pd/C　(20.9%).　The　excellent　ECH　performance　of　Pd@CF　can　be　attributed　to　the　enriched　electrons　on　Pd　surface　resulted　from　the　introduction　of　NH2-R　groups,　which　strengthens　both　the　adsorption　of　benzaldehyde　and　the　adsorbed　hydrogen　(Hads)　on　Pd,　preventing　the　combination　of　Hads　to　form　H2,　that　is,　inhibiting　the　HER.　This　study　gives　a　new　insight　into　design　principles　of　highly　efficient　electrocatalysts　for　the　hydrogenation　of　unsaturated　aldehydes　molecules.　©　2023　Wiley-VCH　GmbH.