Catalytic activity, phase composition, and morphology of binary NiFe metallic systems in CO2 hydrogenation were investigated. High methane yield was detected in the region of high Ni content, except the sample with 75% of Ni which has shown a sharp drop in activity. By means of scanning electron microscopy-energy dispersive X-ray and X-ray diraction methods the dierences in surface structuring of active (Ni80Fe20) and inactive (Ni75Fe25) catalysts were revealed. High methane yield for the former might be explained by defective porous supercial layer of catalyst grains, whereby for the latter the specic surface is diminished due to sintering.