Coupling reactoin of methane and acetonitrile to form high value-added material was studied. The coupling reaction was conducted in non-oxidative condition to attain the target material with high selectivity by preventing the reactants from oxidation. As a result, propionitrile, coupled form of methane and acetonitrile, was produced on Ni/MgO catalyst with avout 35% yield. In this non-oxidative condition, the byproduct due to the oxidation of reactants was not observed and so the selectivity to propionitrile amounted to nearly 100%. Li/MgO catalyst which has been known as a active catalyst for this model reaction in oxkdative condition showed less than 0.2% acetonitrile conversion in the tange of 400℃ ~ 650℃ reaction temperature. Whereas, in this case, the main product was acrylonitrile, dehydrogenated form of propionitrile. In the non-oxidativw coupling reaction of methane and acetonitrile, the rate-determining step was methane activation, and the Ni component doped played a major role in methane activation.