The promoting effect of niobium in a Li/MgO catalyst for the oxidative coupling of methane (OCM) and for the oxidative dehydrogenation of ethane (ODHE) has been studied in some detail. It has been found that a Li/Nb/MgO catalyst with 16 wt % niobium showed the highest activity for the C2 production in the OCM reaction; the activity at 600 °C was ten times that of the Li/MgO catalyst at the same temperature. The Li/Nb/MgO catalyst was also slightly more active for the ODHE reaction than was the Li/MgO catalyst. However, the Li/Nb/MgO catalyst produced considerably more carbon dioxide in the both reactions. Structural investigation of the catalyst showed that the addition of niobium to the Li/MgO catalyst increased the surface area and gave an increase in the lithium content of the calcined catalysts. Two niobium phases, LiNbO3 and Li3NbO4, were formed; it is shown that the first of these probably causes the increased activity. Ageing experiments showed that the activity of the catalyst was lost if the catalyst was used above 720 °C, the melting point of the lithium carbonate phase. The catalyst showed a decrease of surface area after ageing and a sharp decrease of the amount of the two niobium phases. The addition of carbon dioxide to the feed could not prevent the deactivation of the Li/Nb/MgO catalyst.