As a typical greenhouse gas, carbon dioxide (CO2) has significant negative impacts on the environment, and hence, harmless treatment of CO2 has become very important. In this paper, we present a two-step approach for the preparation of three-dimensional graphene-like carbon (3D-GC) from CO2. The 3D-GC sample had abundant micropores and nanopores on the carbon framework and its specific surface area was as high as 927 m2/g. Furthermore, the 3D-GC electrodes showed excellent electrochemical performance when used as the anode material in lithium-ion batteries. The reversible capacity was 705 mA h/g after 100 cycles at 50 mA/g and the rate capability was 252 mA h/g at 5000 mA/g.