In the area of transition-metal catalysis, a modification of supporting ligands is important to not only improve the catalytic activity but also control chemo-, regio-, and stereoselectivity. Although cyclopentadienyl ligands are the most historic ligands in organometallic chemistry, structural diversity has been limited due to difficulties of substitution and complexation without affecting reactive functional groups. For example, in the RhIII-catalyzed C–H bond functionalization, commercially available pentamethylcyclopentadienyl-RhIII (Cp*RhIII) complex has been predominantly employed, and modified CpRhIII complexes have been limited to simple alkyl or phenyl substituted ones. The use of these complexes improved catalytic activity and/or regio-and stereoselectivity. On the other hand, our group developed the synthesis of an ethoxycarbonyl-substituted Cp ligand (CpE) and its reductive complexation to RhCl3. Very recently, our group developed CpRhIII complexes with a pendant amide moiety [CpARhIII]. In this presentation, I will disclose the synthesis and catalytic activity of these new RhIIIcomplexes (CpERhIII and CpARhIII) toward the C–H functionalization.