Storing and hydrogenating CO 2 to CH 4 is an efficient solution to alleviate the greenhouse effect and energy shortage. This work demonstrated that the CaO-captured CO 2 could be selectively converted to CH 4 by Ni-and hydrogenassisted calcium looping (CaL) processes in a batch reactor. The Ni/CaO composite was first synthesized in one step at room temperature by calcium-induced hydrogenation of Ni-mixed calcium carbonate without the use of any solvent and CO 2 emission. The CO 2 capture properties over the Ni/CaO composite and the methanation properties of the Ni/CaCO 3 composite produced after CO 2 capture were then studied in a batch reactor. It was proved that the CO 2 capture properties of CaO can be improved, the CaO recovering temperature can be significantly lowered, and valuable CH 4 can be selectively produced by Ni-and hydrogen-assisted calcium looping processes at moderate/high temperature. The 68.58% methane yield and 100% methane selectivity were achieved under relatively mild conditions. After five Ni-and hydrogen-assisted CaL processes, the methane yield still reaches 45%. This study offers a novel energy-saving CaL process, which can be utilized for facile and selective conversion of the CaO-captured CO 2 to CH 4 .