A 3D graphene oxide/carbon sphere supported silver composite (Ag/GO/C) was synthesized using graphene oxide as the reducing agent. The reducing process of Ag+ was monitored by the ultra violet-visible (UV-vis) absorption spectrometer and the physical properties of the Ag/GO/C composite were characterized by Fourier transform infrared spectrometer (FTIR), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the dispersive Ag nanoparticles are anchored uniformly on the surface of GO sheets with a mean size of about 6.9nm. With introducing carbon black, the Ag nanoparticles aggregated slightly. Compared with its counterpart Ag/GO, the Ag/GO/C composite showed a significantly enhanced activity towards the oxygen reduction reaction in alkaline media. The enhancement can be ascribed to the 3D composite support, which not only improves the electrical conductivity, but also enforces the mass transport in the catalyst layer facilitating the reactants access to the active sites. Moreover, the Ag/GO/C composite exhibits good tolerance to alcohols, carbonates and tetramethylammonium hydroxide. This work is expected to open a new pathway to use GO as a reducing agent to synthesize electrocatalysts without surfactants.