Cp*Rh(III) catalysts have shown excellent performance in the field of inert C-H bond functionalization because of their high activity and stability under mild conditions. However, limited by the number of Rh(III) coordination orbitals, the ligand studies in Cp*Rh(III) catalytic system are relatively few. Recently, our research group has been focusing on the external ligands promoted C-H bond functionalization with high activity and selectivity. In this review, the related works of Cp*Rh(III) catalyzed C-H bond functionalization are systematically summarized, including both symmetric and asymmetric C-H activation, the role of ligands in the Cp*Rh(III) catalytic system is discussed, and some reaction mechanisms are briefly described.