Rhodium-catalyzed C-H bond functionalization via heteroatom-directed C-H bond activation has become a significant area of research in organometallic chemistry. This review highlights the development and application of Rh-catalyzed methods for heteroatom-directed C-H bond functionalization over the past decade. These methods offer advantages over traditional cross-coupling reactions, including atom economy, reduced toxic by-products, and broad synthetic utility. Rh catalysts are particularly effective in C-H bond functionalization due to their functional group tolerance and wide range of applications. The review discusses various mechanisms of Rh-catalyzed C-H bond functionalization, including chelation-assisted functionalization of arenes and intramolecular alkylation. Key examples include the use of pyridine and imine functionalities as directing groups, leading to selective functionalization of specific C-H bonds. The synthesis of complex molecules, such as mescaline analogs and lithospermic acid, demonstrates the utility of these methods in natural product and drug synthesis. The review also covers the development of stereoselective alkylation using chiral auxiliaries and the application of Rh-catalyzed methods in the synthesis of pharmaceuticals, such as a tricyclic indole PKC inhibitor. Directed alkenylation and arylation reactions are discussed, highlighting the use of Rh catalysts in the functionalization of alkenes, alkynes, and arenes. Additionally, the review addresses the challenges and solutions in achieving high enantioselectivity and efficiency in these reactions. The review concludes with the development of new catalyst systems and reaction conditions, including the use of recyclable catalysts and microwave-assisted protocols, which improve the industrial applicability of these methods. Overall, the review emphasizes the importance of Rh-catalyzed C-H bond functionalization in the synthesis of complex molecules and its potential in pharmaceutical and materials chemistry.Rhodium-catalyzed C-H bond functionalization via heteroatom-directed C-H bond activation has become a significant area of research in organometallic chemistry. This review highlights the development and application of Rh-catalyzed methods for heteroatom-directed C-H bond functionalization over the past decade. These methods offer advantages over traditional cross-coupling reactions, including atom economy, reduced toxic by-products, and broad synthetic utility. Rh catalysts are particularly effective in C-H bond functionalization due to their functional group tolerance and wide range of applications. The review discusses various mechanisms of Rh-catalyzed C-H bond functionalization, including chelation-assisted functionalization of arenes and intramolecular alkylation. Key examples include the use of pyridine and imine functionalities as directing groups, leading to selective functionalization of specific C-H bonds. The synthesis of complex molecules, such as mescaline analogs and lithospermic acid, demonstrates the utility of these methods in natural product and drug synthesis. The review also covers the development of stereoselective alkylation using chiral auxiliaries and the application of Rh-catalyzed methods in the synthesis of pharmaceuticals, such as a tricyclic indole PKC inhibitor. Directed alkenylation and arylation reactions are discussed, highlighting the use of Rh catalysts in the functionalization of alkenes, alkynes, and arenes. Additionally, the review addresses the challenges and solutions in achieving high enantioselectivity and efficiency in these reactions. The review concludes with the development of new catalyst systems and reaction conditions, including the use of recyclable catalysts and microwave-assisted protocols, which improve the industrial applicability of these methods. Overall, the review emphasizes the importance of Rh-catalyzed C-H bond functionalization in the synthesis of complex molecules and its potential in pharmaceutical and materials chemistry.