The reaction of propylene oxide and carbon dioxide to propylene carbonate was carried out using Mg-, Ni- and Mg-Ni-containing smectite catalysts which contain different amounts of alkali atoms such as sodium, potassium and lithium. These catalysts are highly active and selective for this reaction. The catalytic activity strongly depends on the elemental composition of the catalyst used. Particularly the amount of alkali atoms incorporated in the catalyst is the most important factor governing the catalytic performance. The most active catalyst among those prepared in the present study shows a turnover number of 105 mmol/g for the propylene carbonate formation, which is the highest turnover number compared with those reported so far (10 mmol/g) for the title reaction.