We have synthesized Rh(I) complexes bearing a 1,2,4-triazol-3-ylidene or imidazol-2-ylidene substituted N-p-toluene-sulfonyl (N-Ts) group. Structural characterizations of the Rh(I) complexes revealed that, because of its mesomeric and inductive electron-withdrawing effects, the N-Ts substituent increased pi-accepting ability and decreased sigma-donating ability of carbenes compared to N-mesityl substituents.