Simple ammonium ionic liquids have been used as a dual catalyst and environmentally benign reaction medium for preparation of dialkoxypropanes, eliminating the need for volatile organic solvents and poisonous hydrogen chloride catalysts. These simple ammonium ionic liquids are air and water stable, easy to synthesise from amine and acid, and relatively cheap, which makes them suitable for industrial application. The results clearly demonstrate that these ionic liquids can be easily separated and reused without losing activity. These ionic liquids provide a good alternative for industrial preparation of dialkoxypropanes.