The present study reports a green synthesis of a new family of ionic liquids (ILs) based on functionalized 4-dimethylaminopyridinium derivatives. The structures of 23 newly synthesized ILs ( 2– 24) were confirmed by FT-IR, 1H-, 13C-, 11B-, 19F-, and 31P-NMR spectroscopy and mass spectrometry. The antimicrobial activity of all novel ILs was tested against a panel of bacteria and fungi. The results prove that all tested ILs are effective antibacterial and antifungal agents, especially 4-(dimethylamino)-1-(4-phenoxybutyl)pyridinium derivatives 5 and 19.