Recently extensive research has focused on replacing toxic hydrazine, monomethylhydrazine, and unsymmetrical dimethylhydrazine as liquid propellant fuels. 2-Azido-N,N-dimethylethylamine (1) is a good candidate to replace hydrazine derivatives in certain hypergolic fuel applications. Energetic ionic liquids that contain the 2-azido-N,N,N-trimethylethylammonium cation with nitrocyanamide, dicyanamide, dinitramide, or azide anion have been successfully synthesized in good yields by metathesis reactions. Ionic liquids have received considerable attention as energetic materials. The replacement of hydrazine with tertiary ammonium salts is especially attractive since many ionic liquids are models for green chemistry. In this work, new azide-functionalized ionic liquids are demonstrated to exhibit hypergolic activity with such oxidizers as 100% nitric acid or nitrogen tetraoxide (NTO).