A novel imidazolium-based ionic liquid-supported hypervalent iodine reagent has been synthesized and employed for a ‘catch and release’ strategy with substituted acetophenones to generate various α-substituted acetophenones in good to excellent yields. The use of an ionic liquid-supported hypervalent iodine reagent avoids chromatographic separation for the purification of α-substituted acetophenones and thus makes the method greener.