Synthetic smectite-like porous materials including Ni2+, Co2+, Mg2+, and Zn2+ cations in the octahedral sheets were used as catalysts and supports for gas-phase hydrogenation of acetonitrile. The Ni2+-containing material itself was active even in the absence of additional active components, while the others were inactive in common with silica, alumina, and NaY zeolite. When platinum was loaded, the smectite-like materials, except those containing Zn2+, exhibited hydrogenation activity, and the platinum-loaded Ni2+-containing material was most active. These catalysts produced a mixture of primary, secondary, and tertiary amines in different selectivities, in contrast to silica-supported platinum catalyst producing mainly tertiary amine. With platinum-loaded Ni2+-containing material, the activity and selectivity can be controlled by changing reduction temperature.