In this study, various types of ionic liquids (ILs) were examined for catalytic activity in the pyrolysis of cellulose for the production of levoglucosenone, which is a valuable and versatile compound for the synthesis of a variety of novel compounds. Cellulose was simply mixed with the ILs and subjected for the pyrolysis, typically at 300 °C, to produce volatile products, including levoglucosenone, separated from the ILs phase. The type of IL anion significantly affected the catalysis, and the use of ILs bearing sulfonate anion resulted in distinguished yields of levoglucosenone and IL recoveries for the reutilization. Detailed thermogravimetric analysis and discussion on properties of ILs revealed the active and thermally stable nature of the sulfonate ILs. Catalytic pyrolysis with those ILs was applied to the conversion of other saccharides composed of glucose molecules, resulting in a preferential formation of levoglucosenone but at low yields as compared to that from cellulose.