Owing to the unique advantages of ionic liquids, the preparation and industrial application of ionic liquids have attracted considerable interest. Herein, we report that a series of simple ammonium ionic liquids has been synthesized and characterised. These ionic liquids are air and water stable, easy to prepare from amine and acid, and relatively cheap. They have been used as catalysts and environmentally benign solvents for the cracking reactions of dialkoxypropanes, eliminating the need for volatile organic solvents and additional catalysts. The results clearly demonstrate that these ionic liquids can be easily separated and reused without losing their activity and quality. Furthermore, the conversion and selectivity obtained with this method are significantly increased in comparison with those reported in traditional organic solvents to date. These ionic liquids provide a good alternative way for the synthesis of alkoxypropenes.