Ni@Pd/C catalysts were synthesized, using Ni/C with different crystalline structures prepared with various ligands. A series of characterizations were performed by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy. The results indicated the electrocatalysts with amorphous/crystalline (denoted as Ni-a and Ni-c) Ni structures decorated with Pd. The formic acid electrocatalytic oxidation results showed that the peak current of Ni-a@Pd/C was about 1.2 times higher than that of Ni-c@Pd/C. The good electrochemical performance and stability of Pd-modified amorphous Ni substrate reveals that the core structure plays an important role in the electrocatalytic activity and the change of the structure can improve the activity and stability of electrocatalysts. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.