A new kind of solid looping material, NiO/NiAl2O4, was synthesized based on integration of NiO, as solid reactant, with a composite metal oxide of NiAl2O4, as a binder, for applying it to chemical-looping combustion. The chemical looping combustion including reduction (fuel with metal) and oxidation (air with the reduced metal oxide) could make a breakthrough in simultaneous contribution to both energy and environmental issues. The reactivity of the reduction and oxidation was investigated by TGA (thermogravimetrical analysis). The results obtained here indicated that the new looping material, NiO/NiAl2O4, might significantly improve reaction rate, conversion, and regenerability in cyclic reaction, compared with the other materials. In addition, the carbon deposition can be completely avoided by addition of water vapor at a ratio of H2O/CH4 = 2.0. These results suggest that this new looping material of NiO/NiAl2O4 may play a vital role in developing chemical-looping combustion.