A tunable rhodium‐catalyzed intramolecular alkyne insertion reaction proceeding through the CC cleavage of benzocyclobutenones is described. Selective formation of either the direct or decarbonylative insertion product can be controlled by using different catalytic systems. A variety of fused β‐naphthol and indene scaffolds were obtained in good yields with high functional group tolerance. This work illustrates a divergent approach to synthesize fused‐ring systems by CC activation/functionalization. Cat. in control: A tunable rhodium‐catalyzed intramolecular alkyne insertion reaction proceeding through CC cleavage of benzocyclobutenones is described. Selective formation of either the direct or decarbonylative insertion product can be controlled by using different catalytic systems. A variety of fused β‐naphthol and indene scaffolds were obtained in good yields with high functional‐group tolerance.