In this review, recent advances in the utilization of two classes of rhodium catalysts - namely rhodium(I) and rhodium(III) - in complexation with chiral cyclopentadienyl and phosphorus ligands in inter-and intramolecular asymmetric C-H bond activation/functionalization of aromatic and vinylic compounds is discussed. Because Rh complexes have been shown to be excellent catalysts for enantioselective alkylation, olefination and allylation of pi systems through directed C-H functionalization under very mild conditions, this method has been seen to have broad synthetic potential both in organic chemistry and in biological systems. Moreover, selective conversion of ubiquitous C-H bonds into functional groups without intermediate preactivation is useful for shortening reaction sequences, with high environmental and economic benefits.