In the realm of transition-metal catalyzed arene functionalization, rhodium(III) catalysis is considered as exemplary due to its propensity to activate C−H bonds to obtain comprehensive molecular assembly. Herein, we demonstrate a new rhodium(III) catalyzed assembly of polyheterocyclic scaffolds via C−H activation and regioselective annulation of 4-arylbut-3-yn-1-amines with 4-hydroxy-2-alkynoates. Heterocyclization and transmetalation prior to annulation is the key for initiation of this relay redox-neutral catalytic cascade.