This work reports the development of a facile, one-step microwave heating method for the synthesis of graphene-supported Pd1Pt3 (Pd core/Pt shell) electrocatalysts. The structure and composition of the synthesized nanocomposites were characterized via transmission electron microscopy and atomic force microscopy as well as energy-dispersive X-ray, X-ray powder diffraction, FTIR, and Raman spectroscopies. Using voltammetry, the electrocatalytic characteristics of the graphene-supported Pd1Pt3 nanostructures were evaluated for the oxidation of methanol as a model reaction. The results show that the introduction of graphene increases the electrochemically active surface area of the Pd1Pt3 nanostructures. As compared to the unsupported Pd1Pt3 electrocatalyst, the graphene-supported Pd1Pt3 electrocatalyst exhibited 80% enhancement of the electrocatalytic specific mass current for the oxidation of methanol. This method may serve as a general, facile approach for the synthesis of graphene-supported bimetallic PtM electrocatalysts with increased utilization of the Pt metal, which is expected to have promising applications in fuel cells.