An unprecedented strategy for Rh-catalyzed C-H activation/C═C bond cleavage of enaminones is described for the construction of biologically interesting aza-spiro α-tetralones and benzo[e]isoindoles. This protocol provides diversely functionalized aza-spiro α-tetralones and benzo[e]isoindoles in good yields via a [4 + 2] annulation of the exomaleimides and maleimides. This strategy displays a good substrate scope, outstanding functional group tolerance, and excellent regioselectivity.