Adjusting the surface structures and electronic structures of metal nanocrystals (NCs) by the metal-organic interface interaction is an emerging strategy to enhance their electrocatalytic behavior. In this work, the D-phenylalanine-functionalized graphene (DPHE-GS) anchoring Pd NCs (denoted as Pd/DPHE-GS) was fabricated via the diazo-reaction followed by a simple chemical reduction. Owing to the metal-organic interface interaction between Pd NCs and DPHE, the size, distribution and electronic structures of Pd NCs on the surface of DPHE-GS can be adjusted. Therefore, the Pd/DPHE-GS shows the highest electrocatalytic activity and the most robust long-term durability and stability towards methanol and ethanol oxidation reaction (MOR and EOR) compared to the commercial Pd/C and other counterparts. This work presents an effective interface engineering strategy to enhance electrocatalytic property. (C) 2020 Elsevier Inc. All rights reserved.