PdCoNi nanocomposites supported on graphene (PdCoNi/G) have been obtained from chemical reduction of metal catalysts and graphite oxide (GO) with a strong reducing agent, followed by calcination at high temperature under N2 condition, and used for electrooxidation of methanol in direct methanol fuel cell. The morphologies and structural properties of electrocatalysts were examined by scanning electron microscopy (SEM) and X-ray diffraction (XRD). X-ray spectroscopy techniques (X-ray photoelectron spectroscopy XPS) was used to investigate the chemical state of the synthesized catalysts. The results of Pd XPS spectra showed the metallic Pd and PdO phases for precalcined and calcined PdCoNi/G nanocomposite, respectively. The X-ray measurement of Co and Ni displayed the various metallic oxides in synthesized electrocatalysts. For electrochemical analysis, cyclic voltammetry (CV) and chronoamperometry (CA) indicated that the PdCoNi/G nanocomposites enhanced the methanol oxidation, compared to the lower activity in the calcined electrocatalysts.