Progress in microwave (MW) energy application technology has stimulated remarkable advances in manufacturing and high-quality applications of ionic liquids (ILs) that are generally used as novel media in chemical engineering. This Review focuses on an emerging technology via the combination of MW energy and the usage of ILs, termed microwave-assisted ionic liquid (MAIL) technology. In comparison to conventional routes that rely on heat transfer through media, the contactless and unique MW heating exploits the electromagnetic wave-ions interactions to deliver energy to IL molecules, accelerating the process of material synthesis, catalytic reactions, and so on. In addition to the inherent advantages of ILs, including outstanding solubility, and well-tuned thermophysical properties, MAIL technology has exhibited great potential in process intensification to meet the requirement of efficient, economic chemical production. Here we start with an introduction to principles of MW heating, highlighting fundamental mechanisms of MW induced process intensification based on ILs. Next, the synergies of MW energy and ILs employed in materials synthesis, as well as their merits, are documented. The emerging applications of MAIL technologies are summarized in the next sections, involving tumor therapy, organic catalysis, separations, and bioconversions. Finally, the current challenges and future opportunities of this emerging technology are discussed.