In the present study, NiO modified ZnAl2O4 and ZnO modified NiAl2O4 spinel along with pure Al2O3, ZnAl2O4 and NiAl2O4 for comparison in the CO2 hydrogenation reaction have been investigated. It was found that NiAl2O4, NiO/ZnAl2O4 and ZnO/NiAl2O4 catalysts exhibited outstanding activity and selectivity towards methane even at high temperature compared to similar spinel structures reported in the literature. NiO/ZnAl2O4 catalyst showed CO2 consumption rate of ~ 19 mu mol/gGreek ano teleias at 600 degrees C and ~ 85% as well as ~ 50% of methane selectivity at 450 degrees C and 600 degrees C, respectively. The high activity and selectivity of methane can be attributed to the presence of metallic Ni and Ni/NiO/ZnAl2O4 interface under the reaction conditions as evidenced by the XRD results. Graphic High performance Ni-Zn-Al-based oxide/spinel nanostructures is synthesized and NiO/ZnAl2O4 catalyst exhibited higher catalytic activity in the CO2 hydrogenation reaction due to the presence of metal support interaction between Ni and ZnAl2O4 support.