Pd/C electrocatalysts containing VN with different morphology (particles (Pd-VN(particles)/C) and plates (Pd-VN(plates)/C)) were prepared by a simple reduction with sodium borohydride and their electrocatalytic performance for methanol oxidation was investigated. The Pd-VN(particles)/C and Pd-VN(plates)/C performed better activity, stronger resistance to CO poisoning and higher stability for methanol oxidation compared with Pd/C by the measurements of cyclic voltammograms (CVs), CO stripping voltammetry and chronoamperometry (CA), respectively. The X-ray photoelectron spectroscopy (XPS), linear sweep voltammetry (LSV) and electrochemical impedance spectrums (EIS) tests were conducted for exploring the role of VN. It is found that the promotion effects of VN can be explained by a bifunctional mechanism and the increase in metallic Pd in electrocatalysts containing VN. Furthermore, the different promotive extents between the VN with different morphology are attributed to the differences of the crystallinity and contact situation of Pd and VN.