A one-step preparation method for indenone derivatives via rhodium-catalyzed decarbonylative cycloadditions of 1H-indene-1,2,3-triones and alkynes has been achieved. [Rh(COD)Cl]₂ with a bisphosphine rac-BINAP ligand was the most efficient catalytic system for this C-C bond activation reaction. The selectivity of indenone can be enhanced by adding copper chloride as an additive. Under the optimized experimental conditions, the indenone compound can be obtained in 87% yield. This reaction is suitable for a broad range of alkynes and a variety of indenone derivatives were obtained in high yields.