For the first time, Pd and PdCo alloy nanoparticles supported on polypropylenimine dendrimer-grafted graphene (Pd and PdCo/PPI-g-G) are prepared and characterized with Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The electrocatalytic activity of Pd and PdCo/PPI-g-G are investigated in terms of formic acid electrooxidation in H2SO4 aqueous solution. The PdCo/PPI-g-G shows much higher formic acid oxidation activities in comparison with Pd/PPI-g-G, and it is more resistant to the surface poisoning. This improved electrocatalytic performance may be due to the fine dispersion of PdCo alloy nanoparticles and bi-functional effect. The kinetic parameters such as charge transfer coefficient and the diffusion coefficient of formic acid are estimated under the quasi steady-state conditions.