Rhenium-catalyzed aryl-acylcyclization. A range of functionalized organomagnesium halides and enol lactones underwent rhenium-catalyzed sequential aryl-acylcyclization under remarkably mild reaction conditions, thus providing an expedient route to polyfunctionalized indenones with complete control of regioselectivity. This approach features its broad substrate scope, excellent functional group tolerance, and synthetic utility in the straightforward synthesis of biologically relevant molecules.