The present work describes an efficient one-pot synthesis of second-generation ionic liquids (ILs), combining in one step the Menshutkin reaction and anion metathesis. Working in a closed vessel under microwaves, or better still under simultaneous ultrasound and/or microwave irradiation, in a few minutes a series of ILs with 1-methylimidazole or pyridine cores were obtained in high yields (80–97% isolated). Under conventional heating, ILs could not be prepared in one pot in acceptable times and yields, whereas our protocol, carried out with commercially available equipment, was highly effective and reproducible. Moreover, ¹H NMR analysis and ion-exchange chromatography showed that the present solventless procedure afforded satisfyingly pure ILs.