Starting from N-trifluoromethyl benzimidazole (1), a series of N-trifluoromethyl benzimidazolium salts 2a–f·HA have been prepared and fully characterized. These were engaged in the formation of Ir­(CO)2(NHC)­Cl, Rh­(COD)­(NHC)­Cl, Se­(NHC), and Au­(NHC)­Cl derivatives. IR analysis of Ir­(CO)2(NHC)­Cl complexes revealed that the trifluoromethyl substituent on nitrogen significantly decreases the σ-donating ability of the carbene carbon. On the other hand, the π-acceptor property of these novel ligands is enhanced. Examination of the 77Se NMR resonance of Se­(NHC) adducts and the redox potentials of Rh­(NHC)­(COD)­Cl complexes further supports this assumption. In addition, the efficiency of these new N-trifluoromethyl NHC ligands was investigated in π-acidic Au­(I)-catalyzed hydroalkoxylation of cyclohexene. The gold complexes bearing NHCs 2a and 2c–e compete with Au­(PPh3)­Cl in terms of catalytic activity.