In this work, we report a low-cost technique for fabrication of a simple three-dimensional (3D) free-standing nickel nanoparticle/graphene aerogel with a graphene sheet network. The 3D composite architecture was formed through the self-assembly aggregation of graphene accompanied by nickel nanoparticle in situ loading on the graphene sheet during the hydrothermal reduction of graphene oxide and Ni ions. The obtained composite architecture was characterized using X-ray diffraction, Fourier transform infrared, and scanning electron microscopy. The electrocatalytic properties of the as-synthesized Ni/graphene aerogel for ethanol oxidation were investigated using cyclic voltammetry and chronoamperometry. A high peak current density of about 6 mA cm<sup>-2</sup> for ethanol oxidation was recorded during ethanol oxidation under the test condition of adding 0.1 M ethanol in 0.1 M NaOH solution. This result revealed excellent electrocatalytic activity for ethanol oxidation, which shows great potential for direct application in ethanol fuel cells. This study provides a guide to preparing well-defined sponge-like three-dimensional metallic/graphene nanoarchitectures for fuel cell applications.