We synthesized a series of mixed ligated tris(amidinate)dimolybdenum complexes, namely, [Mo-2(DAniF)(3)(L)] [DAniF = N,N '-di(p-anisyl)formamidinate; L = acetate (OAc; 1a), m-diphenylphosphino benzoate (m-PPh(2)Bz; lb), nicotinate (Nico; 1c), benzoate (Bi; 1d), 3-furoate (3-Furo; le), isonicotinate (IsoNico; If), and trifluoromethanesulfonate (OTf; lg)], which served as catalysts for radical addition of CCl4 to 1-hexene to give 1,1,1,3-tetrachloroheptane. These mixed ligated complexes la-g afforded the higher yield of the radical addition product than a homoleptic DAniF complex, [Mo-2(DAniF)(4)] (2). Among them, complexes la and Ig gave the radical addition product quantitatively after 9 h with a short induction period. When complexes la and lg were treated with CCl4, we detected the mixed valence Mo-2(II/III) complex, [Mo-2(DAniF)(3)Cl-2] (4), in electrospray ionization mass spectrometry measurements, indicating that the leaving nature of the L ligands was a crucial factor for initiating the catalytic reaction: the catalytic activity of the carboxylate-bridged complex la and the triflate-bridged complex 1g in the initial 30 min highly depended on the ligand-exchange rate of L, as estimated by monitoring the reaction with CCl4 in pyridine, giving the pyridine adduct complex, [Mo-2(DAniF)(3)Cl(py)] (3).