Catalytic decarbonylation of methyl formate has been studied over alkaline metal salts supported on various supports. Active carbon itself and active carbon-supported alkaline metals showed the highest activity values of methyl formate conversion. Magnesia-based catalysts were less active, yet showed better selectivity toward desired decarbonylation with negligible side reactions such as decarboxylation and dimethyl ether formation. The difference between the alkaline metal salts was small. The activity data of the catalysts were correlated fairly well with the amount of strong surface basic sites titrated by temperature-programmed desorption (TPD) of carbon dioxide. The surface acidity measured by ammonia TPD did not show any correlation with the activity. Instead, it appeared to be responsible for the side reactions, and thus to deteriorate the selectivity to decarbonylation