Rhodium-catalyzed oxidative coupling of aromatic substrates with alkynes and alkenes via regioselective C–H bond cleavage has been developed. The key to effective C–H bond activation is the coordination of substituents to the rhodium center. This method enables the construction of various fused-ring systems. The reaction involves the oxidative coupling of aromatic substrates with alkynes and alkenes, utilizing rhodium catalysts and oxidants. The process is efficient and allows for the synthesis of a wide range of π-conjugated molecules. The study highlights the versatility of rhodium catalysis in functionalizing aromatic compounds, particularly those with oxygen- and nitrogen-containing groups. The reactions proceed through mechanisms involving C–H bond cleavage, alkyne insertion, and reductive elimination. The use of different rhodium catalysts and oxidants enables the formation of various coupling products, including isocoumarins, chromones, and isoquinolines. The method is applicable to a variety of substrates, including carboxylic acids, phenols, amides, imines, and heterocycles, demonstrating the broad scope of rhodium-catalyzed oxidative coupling. The study also emphasizes the importance of catalyst design and reaction conditions in achieving high yields and selectivity. Overall, this approach provides a valuable tool for the synthesis of complex organic molecules through efficient and selective C–H bond activation.Rhodium-catalyzed oxidative coupling of aromatic substrates with alkynes and alkenes via regioselective C–H bond cleavage has been developed. The key to effective C–H bond activation is the coordination of substituents to the rhodium center. This method enables the construction of various fused-ring systems. The reaction involves the oxidative coupling of aromatic substrates with alkynes and alkenes, utilizing rhodium catalysts and oxidants. The process is efficient and allows for the synthesis of a wide range of π-conjugated molecules. The study highlights the versatility of rhodium catalysis in functionalizing aromatic compounds, particularly those with oxygen- and nitrogen-containing groups. The reactions proceed through mechanisms involving C–H bond cleavage, alkyne insertion, and reductive elimination. The use of different rhodium catalysts and oxidants enables the formation of various coupling products, including isocoumarins, chromones, and isoquinolines. The method is applicable to a variety of substrates, including carboxylic acids, phenols, amides, imines, and heterocycles, demonstrating the broad scope of rhodium-catalyzed oxidative coupling. The study also emphasizes the importance of catalyst design and reaction conditions in achieving high yields and selectivity. Overall, this approach provides a valuable tool for the synthesis of complex organic molecules through efficient and selective C–H bond activation.